Polyolefin composition with molecular weight maximum occuring in that part of the composition that has the highest comonomer content

ABSTRACT

This invention relates to a polyolefin copolymer composition produced with a catalyst having a metallocene complex in a single reactor in a process for the polymerization of an &amp;agr;olefin monomer with one or more olefin comonomers, and a molecular weight maximum which occurs in that 50 percent by weight of the composition which has the highest weight percent comonomer content. Preferably, the composition has a comonomer partitioning factor C pf which is equal to or greater than 1.10 or molecular weight partitioning factor M pf which is equal to or greater than 1.15. Preferred composition also have at least 0.01 long chain branches per 1000 carbon atoms along the polymer backbone. These compositions with reverse molecular engineering have superior properties and are easily processable due to the simultaneous presence of the association of high molecular weight with high comonomer content and of long chain branching.

FIELD OF THE INVENTION

[0001] This invention relates to polyolefin copolymer compositions withthe molecular weight maximum occurring in that part of the compositionthat has the highest comonomer content, and, preferably, with long chainbranching, which have been produced from an α-olefin monomer and one ormore α-olefin comonomers in a single reactor with a single metallocenecatalyst, and to processes for the production of these materials and thecatalysts used therefor.

BACKGROUND OF THE INVENTION

[0002] Recently there have been many advances in the production ofpolyolefin copolymers due to the introduction of metallocene catalysts.Metallocene catalysts offer the advantage of generally higher activitythan traditional Ziegler catalysts and are usually described ascatalysts which are single-site in nature. Because of their single-sitenature the polyolefin copolymers produced by metallocene catalysts oftenare quite uniform in their molecular structure. For example, incomparison to traditional Ziegler produced materials, they haverelatively narrow molecular weight distributions (MWD) and narrow ShortChain Branching Distribution (SCBD). By narrow SCBD, it is meant thatthe frequency of short chain branches, formed where comonomersincorporate into the polyolefin chain, is relatively independent ofmolecular weight. Although certain properties of metallocene productsare enhanced by narrow MWD, difficulties are often encountered in theprocessing of these materials into useful articles and films relative toZiegler produced materials. In addition, the uniform nature of the SCBDof metallocene produced materials does not readily permit certainstructures to be obtained.

[0003] An approach to improving processability has been the inclusion oflong chain branching (LCB), which is particularly desirable from theviewpoint of improving processability without damaging advantageousproperties. U.S. Pat. Nos. 5,272,236; 5,278,272; 5,380,810; and EP659,773, EP 676,421, WO 94/07930 relate to the production of polyolefinswith long chain branching.

[0004] Another approach is the addition of the polymer processing aidsto the polymer prior to fabrication into films or articles. Thisrequires extra processing and is expensive.

[0005] A different approach to the problem has been to make compositionswhich are blends or mixtures of individual polymeric materials with thegoal being to maximize the beneficial properties while minimizing theprocessing problems. This requires extra processing which increases thecost of materials produced. U.S. Pat. Nos. 4,598,128; 4,547,551;5,408,004; 5,382,630; 5,382,631; and 5,326,602; and WO 94/22948 and WO95/25141 relate to blends.

[0006] Another way to provide a solution for the processability problemsand to vary SCBD has been the development of various cascade processes,where the material is produced by a series of polymerizations underdifferent reactor conditions, such as in a series of reactors.Essentially, a material similar in some ways to a blend is produced,with a modality greater than one for various physical properties, suchas the molecular weight distribution. While polyolefin compositions withsuperior processability characteristics can be produced this way, thesemethods are expensive and complicated relative to the use of a singlereactor. Processes of interest are disclosed in U.S. Pat. No. 5,442,018,WO 95/26990, WO 95/07942 and WO 95/10548.

[0007] Another potentially feasible approach to improving processabilityand varying SCBD has been to use a multicomponent catalyst. In somecases, a catalyst which has a metallocene catalyst and a conventionalZiegler-Natta catalyst on the same support to produce a multimodalmaterial, in other cases two metallocene catalysts have been used inpolyolefin polymerizations. Components of different molecular weightsand compositions are produced in a single reactor operating under asingle set of polymerization conditions. This approach is difficult fromthe point of view of process control and catalyst preparation. Catalystsystems of interest are disclosed in WO 95/11264 and EP 676,418.

SUMMARY OF THE INVENTION

[0008] It would be desirable to be able to produce a polyolefincopolymer composition which has the molecular weight maximum occurringin that portion of the composition that has the highest number of shortchain branches and which is very easy to process. Further, it would bedesirable to be able to accomplish this using a single metallocenecatalyst, preferably supported in a polymerization process using asingle reactor, preferably gas phase, operating semi-continuously or,preferably, continuously under a single set of reactor conditions. Itwould be especially desirable to be able to produce a polyolefincopolymer composition which has the molecular weight maximum occurringin that portion of the composition that has the highest number of shortchain branches and which has significant long chain branching.

[0009] The short chain branching distribution of a polyolefincomposition, which is due to the incorporation of an α-olefin comonomerduring the polymerization of an α-olefin monomer, can be examined byseveral techniques, such as, for example, ATREF-DV and GPC-FTIR. If thematerial of the composition is divided into portions starting at one endof the distribution or the other, the relationship between high shortchain branching content due to high comonomer content and molecularweight can be determined.

[0010] In one embodiment this invention is a polyolefin copolymercomposition produced with a catalyst having a metallocene complex in asingle reactor in a process for the polymerization of an α-olefinmonomer with one or more olefin comonomers, the composition having longchain branches along the polymer backbone and a molecular weight maximumwhich occurs in that 50 percent by weight of the composition which hasthe highest weight percent comonomer content.

[0011] A preferred embodiment of this invention is a polyolefincopolymer composition wherein the composition has a comonomerpartitioning factor C_(pf) which is equal to or greater than 1.10 or amolecular weight partitioning factor M_(pf) which is equal to or greaterthan 1.15, or a comonomer partitioning factor C_(pf) which is equal toor greater than 1.10 and a molecular weight partitioning factor M_(pf)which is equal to or greater than 1.15, where the comonomer partitioningfactor C_(pf) is calculated from the equation:${C_{pf} = \frac{\frac{\frac{\sum\limits_{i = 1}^{n}\quad {w_{i}\quad c_{i}}}{\sum\limits_{i = 1}^{n}\quad w_{i}}}{\sum\limits_{j = 1}^{m}\quad {w_{j} \cdot c_{j}}}}{\sum\limits_{j = 1}^{m}\quad w_{j}}},$

[0012] where c_(i) is the mole fraction comonomer content and w_(i) isthe normalized weight fraction as determined by GPC/FTIR for the n FTIRdata points above the median molecular weight, c_(j) is the molefraction comonomer content and w_(j) is the normalized weight fractionas determined by GPC/FTIR for the m FTIR data points below the medianmolecular weight, wherein only those weight fractions w_(i) or w_(j)which have associated mole fraction comonomer content values are used tocalculate C_(pf) and n and m are greater than or equal to 3; and wherethe molecular weight partitioning factor M_(pf) is calculated from theequation:${M_{pf} = \frac{\frac{\frac{\sum\limits_{i = 1}^{n}\quad {w_{i} \cdot M_{i}}}{\sum\limits_{i = 1}^{n}\quad w_{i}}}{\sum\limits_{j = 1}^{m}\quad {w_{j}\quad M_{j}}}}{\sum\limits_{j = 1}^{m}\quad w_{j}}},$

[0013] where M_(i) is the viscosity average molecular weight and w_(i)is the normalized weight fraction as determined by ATREF-DV for the ndata points in the fractions below the median elution temperature, M_(j)is the viscosity average molecular weight and w_(j) is the normalizedweight fraction as determined by ATREF-DV for the m data points in thefractions above the median elution temperature, wherein only thoseweight fractions, w_(i) or w_(j) which have associated viscosity averagemolecular weights greater than zero are used to calculate M_(pf) and nand m are greater than or equal to 3.

[0014] In another embodiment this invention is a polyolefin copolymercomposition produced with a catalyst having a metallocene complex in asingle reactor in a continuous gas phase process for the polymerizationof an α-olefin monomer with one or more olefin comonomers, thecomposition having a comonomer partitioning factor C_(pf) which is equalto or greater than 1.10, or a molecular weight partitioning factorM_(pf) which is equal to or greater than 1.15, or a comonomerpartitioning factor C_(pf) which is equal to or greater than 1.10 and amolecular weight partitioning factor M_(pf) which is equal to or greaterthan 1.15, where the comonomer partitioning factor C_(pf) and themolecular weight partitioning factor M_(pf) are as previously defined.

[0015] In another embodiment the invention is a polyolefin copolymercomposition produced with a catalyst having a bis-Cp metallocene complexin a single reactor in a process for the polymerization of an α-olefinmonomer with one or more olefin comonomers, the composition having acomonomer partitioning factor C_(pf) which is equal to or greater than1.10, or a molecular weight partitioning factor M_(pf) which is equal toor greater than 1.15, or a comonomer partitioning factor C_(pf) which isequal to or greater than 1.10 and a molecular weight partitioning factorM_(pf) which is equal to or greater than 1.15, where the comonomerpartitioning factor C_(pf) and the molecular weight partitioning factorM_(pf) are as previously defined.

[0016] In a further embodiment this invention is a polyolefin copolymercomposition produced with a catalyst having an organometallic compoundin a single reactor in a process for the polymerization of an α-olefinmonomer with one or more olefin comonomers, the composition having longchain branches along the polymer backbone and a molecular weight maximumwhich occurs in that 50 percent by weight of the composition which hasthe highest weight percent comonomer content.

[0017] Polymerization processes to provide the aforementionedcompositions are within the scope of this invention and one embodimentis a process for the polymerization of an α-olefin monomer with one ormore olefin comonomers using a metallocene catalyst in a single reactor,the composition having long chain branches along the polymer backboneand a molecular weight maximum which occurs in that 50 percent by weightof the composition which has the highest weight percent comonomercontent. A preferred embodiment is that where the composition has acomonomer partitioning factor C_(pf) which is equal to or greater than1.10, or a molecular weight partitioning factor M_(pf) which is equal toor greater than 1.15, or a comonomer partitioning factor C_(pf) which isequal to or greater than 1.10 and a molecular weight partitioning factorM_(pf) which is equal to or greater than 1.15, where the comonomerpartitioning factor C_(pf) and the molecular weight partitioning factorM_(pf) are as previously defined.

[0018] Another embodiment of this invention is a continuous gas phaseprocess for the polymerization of an α-olefin monomer with one or moreolefin comonomers using a catalyst having a metallocene complex in asingle reactor, the process producing a composition having a comonomerpartitioning factor C_(pf) which is equal to or greater than 1.10, or amolecular weight partitioning factor M_(pf) which is equal to or greaterthan 1.15, or a comonomer partitioning factor C_(pf) which is equal toor greater than 1.10 and a molecular weight partitioning factor M_(pf)which is equal to or greater than 1.15, where the comonomer partitioningfactor C_(pf) and the molecular weight partitioning factor M_(pf) are aspreviously defined.

[0019] Another embodiment of this invention is a process for thepolymerization of an α-olefin monomer with one or more olefin comonomersusing a catalyst having a bis-Cp metallocene complex in a singlereactor, the process producing a composition having a comonomerpartitioning factor C_(pf) which is equal to or greater than 1.10, or amolecular weight partitioning factor M_(pf) which is equal to or greaterthan 1.15, or a comonomer partitioning factor C_(pf) which is equal toor greater than 1.10 and a molecular weight partitioning factor M_(pf)which is equal to or greater than 1.15, where the comonomer partitioningfactor C_(pf) and the molecular weight partitioning factor M_(pf) are aspreviously defined.

[0020] A further embodiment of this invention is a process for thepolymerization of an α-olefin monomer with one or more olefin comonomersusing a catalyst having an organometallic compound in a single reactor,the composition having long chain branches along the polymer backboneand a molecular weight maximum which occurs in that 50 percent by weightof the composition which has the highest weight percent comonomercontent.

[0021] Another embodiment of this invention is a process for thepolymerization of an α-olefin monomer with one or more olefin comonomersusing a catalyst having an organometallic compound in a single reactor,the composition having long chain branches along the polymer backboneand a molecular weight maximum which occurs in that 50 percent by weightof the composition which has the highest weight percent comonomercontent.

[0022] The compositions of this invention have desirable properties andcan be easily processed into a film or other article of manufacturewhich has a melt strength of greater than 4 cN, or which has a sealstrength of greater than 1.9 kg (4.2 lb.), or which has a hot tackgreater than 0.23 kg (0.5 lb.), or which has a dart impact strengthgreater than 100 g.

[0023] A further embodiment of this invention relate to a blend of twoor more resin components comprising:

[0024] (A) from about 1 weight percent to about 99 weight percent of apolyolefin copolymer composition produced with a catalyst having ametallocene complex in a single reactor in a process for thepolymerization of an α-olefin monomer with one or more olefincomonomers, the composition having long chain branches along the polymerbackbone and a molecular weight maximum which occurs in that 50 percentby weight of the composition which has the highest weight percentcomonomer content; and

[0025] (B) from about 99 weight percent to about 1 weight percent of oneor more resins that are different from the (A) component.

[0026] Another embodiment of this invention is a blend of two or moreresin components comprising:

[0027] (A) from about 1 weight percent to about 99 weight percent of apolyolefin copolymer composition produced with a catalyst having ametallocene complex in a single reactor in a continuous gas phaseprocess for the polymerization of an α-olefin monomer with one or moreolefin comonomers, the composition having a comonomer partitioningfactor C_(pf) which is equal to or greater than 1.10, or a molecularweight partitioning factor M_(pf) which is equal to or greater than1.15, or a comonomer partitioning factor C_(pf) which is equal to orgreater than 1.10 and a molecular weight partitioning factor M_(pf)which is equal to or greater than 1.15, where the comonomer partitioningfactor C_(pf) and the molecular weight partitioning factor M_(pf) are aspreviously defined; and

[0028] (B) from about 99 weight percent to about 1 weight percent of oneor more resins that are different from the (A) component.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029]FIG. 1 is an ATREF-DV plot for the composition of Example 1.

[0030]FIG. 2 is an ATREF-DV plot for the composition of Example 2.

[0031]FIG. 3 is an ATREF-DV plot for the composition of Example 3.

[0032]FIG. 4 is an ATREF-DV plot for the composition of Example 4.

[0033]FIG. 5 is an ATREF-DV plot for the composition of Example 5.

[0034]FIG. 6 is an ATREF-DV plot for the composition of ComparativeExample D, DOWLEX™ 2056, a commercially available Ziegler-Natta producedpolyethylene.

[0035]FIG. 7 is an ATREF-DV plot for the composition of ComparativeExample A, BP Innovex™ 7209.

[0036]FIG. 8 is an ATREF-DV plot for the composition of ComparativeExample B, Exxon Exceed™ 401.

[0037]FIG. 9 is an ATREF-DV plot for the composition of ComparativeExample E, solution INSITE™ metallocene produced AFFINITY™.

[0038]FIG. 10 is an ATREF-DV plot for the composition of ComparativeExample C, Novacore, a gas phase produced PE.

[0039]FIG. 11 is a plot of GPC-FTIR data for the composition of Example1.

[0040]FIG. 12 is a plot of GPC-FTIR data for the composition of Example2.

[0041]FIG. 13 is a plot of GPC-FTIR data for the composition of Example3.

[0042]FIG. 14 is a plot of GPC-FTIR data for the composition of Example5.

[0043] All references herein to elements or metals belonging to acertain Group refer to the Periodic Table of the Elements published andcopyrighted by CRC Press, Inc., 1989. Also any reference to the Group orGroups shall be to the Group or Groups as reflected in this PeriodicTable of the Elements using the IUPAC system for numbering groups.

[0044] Suitable catalysts for use herein may be derivatives of anytransition metal including Lanthanides, but preferably of Group 3, 4, orLanthanide metals which are in the +2, +3, or +4 formal oxidation state.Preferred compounds include metal complexes containing from one to threeπ-bonded anionic or neutral ligand groups, which may be cyclic ornoncyclic delocalized π-bonded anionic ligand groups. Exemplary of suchπ-bonded anionic ligand groups are conjugated or nonconjugated, cyclicor non-cyclic dienyl groups, allyl groups, and arene groups. By the term“π-bonded” is meant that the ligand group is bonded to the transitionmetal by means of a π bond.

[0045] Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements, and such hydrocarbyl- orhydrocarbyl-substituted metalloid radicals further substituted with aGroup 15 or 16 hetero atom containing moiety. Included within the term“hydrocarbyl” are C₁₋₂₀ straight, branched and cyclic alkyl radicals,C₆₋₂₀ aromatic radicals, C₇₋₂₀ alkyl-substituted aromatic radicals, andC₇₋₂₀ aryl-substituted alkyl radicals. In addition two or more suchradicals may together form a fused ring system, a hydrogenated fusedring system, or a metallocycle with the metal. Suitablehydrocarbyl-substituted organometalloid radicals include mono-, di- andtri-substituted organometalloid radicals of Group 14 elements whereineach of the hydrocarbyl groups contains from 1 to 20 carbon atoms.Examples of suitable hydrocarbyl-substituted organo-metalloid radicalsinclude trimethylsilyl, triethylsilyl, ethyldimethylsilyl,methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamine, phosphine, ether or thioether moieties or divalent derivativesthereof, such as, for example, amide, phosphide, ether or thioethergroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group or to the hydrocarbyl-substituted metalloidcontaining group.

[0046] Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, and decahydroanthracenylgroups, as well as C₁₋₁₀ hydrocarbyl-substituted or C₁₋₁₀hydrocarbyl-substituted silyl substituted derivatives thereof. Preferredanionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.

[0047] A suitable class of catalysts are transition metal complexescorresponding to the formula:

L_(l)MX_(m)X′_(n)X″_(p), or a dimer thereof

[0048] wherein:

[0049] L is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 nonhydrogen atoms, optionally two L groups may bejoined together forming a bridged structure, and further optionally oneL may be bound to X;

[0050] M is a metal of Group 4 of the Periodic Table of the Elements inthe +2, +3 or +4 formal oxidation state;

[0051] X is an optional, divalent substituent of up to 50 nonhydrogenatoms that together with L forms a metallocycle with M;

[0052] X′ is an optional neutral Lewis base having up to 20 non-hydrogenatoms;

[0053] X″ each occurrence is a monovalent, anionic moiety having up to40 nonhydrogen atoms, optionally, two X″ groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or, optionally two X″ groups may be covalently bound together toform a neutral, conjugated or nonconjugated diene that is π-bonded to M(whereupon M is in the +2 oxidation state), or further optionally one ormore X″ and one or more X′ groups may be bonded together thereby forminga moiety that is both covalently bound to M and coordinated thereto bymeans of Lewis base functionality;

[0054] l is 0, 1 or 2;

[0055] m is 0 or 1;

[0056] n is a number from 0 to 3;

[0057] p is an integer from 0 to 3; and

[0058] the sum, l+m+p, is equal to the formal oxidation state of M,except when two X″ groups together form a neutral conjugated ornonconjugated diene that is π-bonded to M, in which case the sum l+m isequal to the formal oxidation state of M.

[0059] Preferred complexes include those containing either one or two Lgroups. The latter complexes include those containing a bridging grouplinking the two L groups. Preferred bridging groups are thosecorresponding to the formula (ER*₂)_(x) wherein E is silicon, germanium,tin, or carbon, R* independently each occurrence is hydrogen or a groupselected from silyl, hydrocarbyl, hydrocarbyloxy and combinationsthereof, said R* having up to 30 carbon or silicon atoms, and x is 1 to8. Preferably, R* independently each occurrence is methyl, ethyl,propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

[0060] Examples of the complexes containing two L groups are compoundscorresponding to the formula:

[0061] wherein:

[0062] M is zirconium, zirconium or hafnium, preferably zirconium orhafnium, in the +2 or +4 formal oxidation state;

[0063] R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 nonhydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system; and

[0064] X″ independently each occurrence is an anionic ligand group of upto 40 nonhydrogen atoms, or two X″ groups together form a divalentanionic ligand group of up to 40 nonhydrogen atoms or together are aconjugated diene having from 4 to 30 nonhydrogen atoms forming aπ-complex with M, whereupon M is in the +2 formal oxidation state; and

[0065] R*, E and x are as previously defined.

[0066] The foregoing metal complexes are especially suited for thepreparation of polymers having stereoregular molecular structure. Insuch capacity it is preferred that the complex possesses C_(s) symmetryor possesses a chiral, stereorigid structure. Examples of the first typeare compounds possessing different delocalized π-bonded systems, such asone cyclopentadienyl group and one fluorenyl group. Similar systemsbased on Ti(IV) or Zr(IV) were disclosed for preparation of syndiotacticolefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256(1980). Examples of chiral structures include rac bis-indenyl complexes.Similar systems based on Ti(IV) or Zr(IV) were disclosed for preparationof isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232,233-47, (1982).

[0067] Exemplary bridged ligands containing two π-bonded groups are:(dimethylsilyl-bis(cyclopentadienyl)),(dimethylsilyl-bis(methylcyclopentadienyl)),(dimethylsilyl-bis(ethylcyclopentadienyl)),(dimethylsilyl-bis(t-butylcyclopentadienyl)),(dimethylsilyl-bis(tetramethylcyclopentadienyl)),(dimethylsilyl-bis(indenyl)), (dimethylsilyl-bis(tetrahydroindenyl)),(dimethylsilyl-bis(fluorenyl)),(dimethylsilyl-bis(tetrahydrofluorenyl)),(dimethylsilyl-bis(2-methyl-4-phenylindenyl)),(dimethylsilyl-bis(2-methylindenyl)),(dimethylsilyl-cyclopentadienyl-fluorenyl),(dimethylsilyl-cyclopentadienyl-octahydrofluorenyl),(dimethylsilyl-cyclopentadienyl-tetrahydrofluorenyl),(1,1,2,2-tetramethyl-1, 2-disilyl-bis-cyclopentadienyl),(1,2-bis(cyclopentadienyl)ethane, and(isopropylidene-cyclopentadienyl-fluorenyl).

[0068] Preferred X″ groups are selected from hydride, hydrocarbyl,silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

[0069] A further class of metal complexes utilized in the presentinvention corresponds to the preceding formula L_(l)MX_(m)X′_(n)X″_(p),or a dimer thereof, wherein X is a divalent substituent of up to 50nonhydrogen atoms that together with L forms a metallocycle with M.

[0070] Preferred divalent X substituents include groups containing up to30 nonhydrogen atoms comprising at least one atom that is oxygen,sulfur, boron or a member of Group 14 of the Periodic Table of theElements directly attached to the delocalized π-bonded group, and adifferent atom, selected from the group consisting of nitrogen,phosphorus, oxygen or sulfur that is covalently bonded to M.

[0071] A preferred class of such Group 4 metal coordination complexesused according to the present invention corresponds to the formula:

[0072] wherein:

[0073] M is titanium or zirconium in the +2 or +4 formal oxidationstate;

[0074] R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 nonhydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system;

[0075] each X″ is a halo, hydrocarbyl, hydrocarbyloxy or silyl group,said group having up to 20 nonhydrogen atoms, or two X″ groups togetherform a neutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

[0076] Y is —O—, —S—, —NR*—, —PR*—; and

[0077] Z is SiR*₂, CR*₂, SiR*₂SiR*₂, CR*₂CR*₂, CR*═CR*, CR*₂SiR*₂, orGeR*₂, wherein R* is as previously defined.

[0078] An especially preferred group of transition metal complexes foruse in the catalysts of this invention are those disclosed in U.S. Pat.No. 5,470,993, incorporated herein by reference, which correspond to theformula:

[0079] wherein:

[0080] M is titanium or zirconium in the +2 formal oxidation state;

[0081] L is a group containing a cyclic, delocalized anionic, π-systemthrough which the group is bound to M, and which group is also bound toZ;

[0082] Z is a moiety bound to M via σ-bond, comprising boron, and themembers of Group 14 of the Periodic Table of the Elements, and alsocomprising an element selected from the groups consisting of an elementselected from the groups consisting of nitrogen, phosphorus, sulfur andoxygen, said moiety having up to 60 nonhydrogen atoms; and

[0083] X is a neutral, conjugated or nonconjugated diene, optionallysubstituted with one or more groups selected from hydrocarbyl ortrimethylsilyl groups, said X having up to 40 carbon atoms and forming aπ-complex with M.

[0084] Illustrative Group 4 metal complexes that may be employed in thepractice of the present invention include:

[0085] cyclopentadienyltitaniumtrimethyl,

[0086] cyclopentadienyltitaniumtriethyl,

[0087] cyclopentadienyltitaniumtriisopropyl,

[0088] cyclopentadienyltitaniumtriphenyl,

[0089] cyclopentadienyltitaniumtribenzyl,

[0090] cyclopentadienyltitanium-2,4-dimethylpentadienyl,

[0091]cyclopentadienyltitanium-2,4-dimethylpentadienyl·triethylphosphine,

[0092]cyclopentadienyltitanium-2,4-dimethylpentadienyl·trimethylphosphine,

[0093] cyclopentadienyltitaniumdimethylmethoxide,

[0094] cyclopentadienyltitaniumdimethylchloride,

[0095] pentamethylcyclopentadienyltitaniumtrimethyl,

[0096] indenyltitaniumtrimethyl,

[0097] indenyltitaniumtriethyl,

[0098] indenyltitaniumtripropyl,

[0099] indenyltitaniumtriphenyl,

[0100] tetrahydroindenyltitaniumtribenzyl,

[0101] pentamethylcyclopentadienyltitaniumtriisopropyl,

[0102] pentamethylcyclopentadienyltitaniumtribenzyl,

[0103] pentamethylcyclopentadienyltitaniumdimethylmethoxide,

[0104] pentamethylcyclopentadienyltitaniumdimethylchloride,

[0105] bis(η⁵-2,4-dimethylpentadienyl)titanium,

[0106] bis(η⁵-2,4-dimethylpentadienyl)titanium·trimethylphosphine,

[0107] bis(η⁵-2,4-dimethylpentadienyl)titanium·triethylphosphine,

[0108] octahydrofluorenyltitaniumtrimethyl,

[0109] tetrahydroindenyltitaniumtrimethyl,

[0110] tetrahydrofluorenyltitaniumtrimethyl,

[0111](tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

[0112](tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,

[0113](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdibenzyl,

[0114](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl,

[0115](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitaniumdimethyl,

[0116] (tert-butylamido) (tetramethyl-η⁵-indenyl)dimethylsilanetitaniumdimethyl,

[0117] (tert-butylamido) (tetramethyl-η⁵-cyclopentadienyl)dimethylsilane

[0118] titanium (III) 2-(dimethylamino)benzyl; (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) allyl,

[0119](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl,

[0120] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)1,4-diphenyl-1,3-butadiene,

[0121] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)1,3-pentadiene,

[0122] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

[0123] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)2,4-hexadiene,

[0124] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

[0125] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)isoprene,

[0126] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

[0127] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)2,3-dimethyl-1,3-butadiene,

[0128] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)isoprene

[0129] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dimethyl

[0130] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)dibenzyl

[0131] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

[0132] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

[0133] (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

[0134] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

[0135] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dimethyl,

[0136] (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)dibenzyl,

[0137] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0138] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene,

[0139] (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene,

[0140] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (IV)1,3-butadiene,

[0141] (tert-butylamido) (tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (IV) 2,3-dimethyl-1,3-butadiene,

[0142](tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium(IV) isoprene,

[0143] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)1,4-dibenzyl-1,3-butadiene,

[0144] (tert-butylamido) (tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II) 2,4-hexadiene,

[0145] (tert-butylamido) (tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II) 3-methyl-1,3-pentadiene,

[0146](tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethyl-silanetitaniumdimethyl,

[0147](tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethyl-silanetitaniumdimethyl,

[0148](tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,

[0149](tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl

[0150] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)methylphenyl-silanetitanium (IV)dimethyl,

[0151] (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)methylphenyl-silanetitanium (II)1,4-diphenyl-1,3-butadiene,

[0152] 1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyl-titanium (IV) dimethyl, and

[0153]1-(tert-butylamido)-2-(tetramethyl-η⁵-cyclopentadienyl)ethanediyl-titanium(II) 1,4-diphenyl-1,3-butadiene.

[0154] Complexes containing two L groups including bridged complexessuitable for use in the present invention include:

[0155] bis(cyclopentadienyl)zirconiumdimethyl,

[0156] bis(cyclopentadienyl)zirconium dibenzyl,

[0157] bis(cyclopentadienyl)zirconium methyl benzyl,

[0158] bis(cyclopentadienyl)zirconium methyl phenyl,

[0159] bis(cyclopentadienyl)zirconiumdiphenyl,

[0160] bis(cyclopentadienyl)titanium-allyl,

[0161] bis(cyclopentadienyl)zirconiummethylmethoxide,

[0162] bis(cyclopentadienyl)zirconiummethylchloride,

[0163] bis (pentamethylcyclopentadienyl)zirconiumdimethyl,

[0164] bis(pentamethylcyclopentadienyl)titaniumdimethyl,

[0165] bis(indenyl)zirconiumdimethyl,

[0166] indenylfluorenylzirconiumdimethyl,

[0167] bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),

[0168] bis(indenyl)zirconium methyltrimethylsilyl,

[0169] bis(tetrahydroindenyl)zirconium methyltrimethylsilyl,

[0170] bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,

[0171] bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,

[0172] bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,

[0173] bis(pentamethylcyclopentadienyl)zirconiummethylchloride,

[0174] bis(methylethylcyclopentadienyl)zirconiumdimethyl,

[0175] bis(butylcyclopentadienyl)zirconium dibenzyl,

[0176] bis(t-butylcyclopentadienyl)zirconiumdimethyl,

[0177] bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,

[0178] bis(methylpropylcyclopentadienyl)zirconium dibenzyl,

[0179] bis(trimethylsilylcyclopentadienyl)zirconium dibenzyl,

[0180] dimethylsilyl-bis(cyclopentadienyl)zirconiumdimethyl,

[0181] dimethylsilyl-bis(tetramethylcyclopentadienyl)titanium-(III)allyl

[0182] dimethylsilyl-bis(t-butylcyclopentadienyl)zirconiumdichloride,

[0183] dimethylsilyl-bis(n-butylcyclopentadienyl)zirconiumdichloride,

[0184] methylene-bis(tetramethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

[0185] methylene-bis(n-butylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

[0186] dimethylsilyl-bis(indenyl)zirconiumbenzylchloride,

[0187] dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl,

[0188] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconiumdimethyl,

[0189]dimethylsilyl-bis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

[0190] dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

[0191] dimethylsilyl-bis(tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

[0192] dimethylsilyl-bis(fluorenyl)zirconiummethylchloride,

[0193] dimethylsilyl-bis(tetrahydrofluorenyl)zirconiumbis(trimethylsilyl),

[0194] (isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl,and

[0195] dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconiumdimethyl.

[0196] An especially preferred bis-CP complex for use in the catalystsuseful in this invention are the bridged bis-Cp complexes of EP 676,421which correspond to the formula:

[0197] wherein

[0198] Cp¹, Cp² are independently a substituted or unsubstituted indenylor hydrogenated indenyl group;

[0199] Y is a univalent anionic ligand, or Y₂ is a diene;

[0200] M is zirconium, titanium or hafnium; and

[0201] Z is a bridging group comprising an alkylene group having 1 to 20carbon atoms or a dialkyl silyl- or germyl-group, or alkyl phosphine oramine radical.

[0202] Other catalysts, especially catalysts containing other Group 4metals, will, of course, be apparent to those skilled in the art. A widevariety of organometallic compounds, including nonmetallocenes, whichare useful in this invention are also apparent to those skilled in theart.

[0203] The complexes are rendered catalytically active by combinationwith an activating cocatalyst or by use of an activating technique.Suitable activating cocatalysts for use herein include polymeric oroligomeric alumoxanes, especially methylalumoxane, triisobutylaluminum-modified methylalumoxane, or diisobutylalumoxane; strong Lewisacids, such as C₁₋₃₀ hydrocarbyl substituted Group 13 compounds,especially tri(hydrocarbyl)aluminum—or tri(hydrocarbyl)boron—compoundsand halogenated derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, especiallytris(pentafluorophenyl)borane; and nonpolymeric, inert, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions). A suitable activating techniqueis bulk electrolysis (explained in more detail hereinafter).Combinations of the foregoing activating cocatalysts and techniques mayalso be employed if desired. The foregoing activating cocatalysts andactivating techniques have been previously taught with respect todifferent metal complexes in the following references: EP-A-277,003;U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,064,802; EP-A-468,651(equivalent to U.S. Ser. No. 07/547,718); EP-A-520,732 (equivalent toU.S. Ser. No. 07/876,268); and WO 93/23412 (equivalent to U.S. Ser. No.07/884,966 filed May 1, 1992); the teachings of which are herebyincorporated by reference.

[0204] Suitable nonpolymeric, inert, compatible, noncoordinating, ionforming compounds useful as cocatalysts in one embodiment of the presentinvention comprise a cation which is a Bronsted acid capable of donatinga proton, and a compatible, noncoordinating, anion, A⁻. Preferred anionsare those containing a single coordination complex comprising acharge-bearing metal or metalloid core which anion is capable ofbalancing the charge of the active catalyst species (the metal cation)which is formed when the two components are combined. Also, said anioncan be displaced by olefinic, diolefinic and acetylenically unsaturatedcompounds or other neutral Lewis bases such as ethers or nitrites.Suitable metals include, but are not limited to, aluminum, gold andplatinum. Suitable metalloids include, but are not limited to, boron,phosphorus, and silicon. Compounds containing anions which comprisecoordination complexes containing a single metal or metalloid atom arewell known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

[0205] Preferably such cocatalysts may be represented by the followinggeneral formula:

(L*−H)⁺ _(d) A^(d−)

[0206] wherein:

[0207] L* is a neutral Lewis base;

[0208] (L*−H)⁺is a Bronsted acid;

[0209] A^(d−) is a noncoordinating, compatible anion having a charge ofd−; and

[0210] d is an integer from 1 to 3.

[0211] More preferably d is one, that is, A^(d−) is A⁻.

[0212] Highly preferably, A⁻ corresponds to the formula:

[BQ₄]³¹

[0213] wherein:

[0214] B is boron in the +3 formal oxidation state; and

[0215] Q independently each occurrence is selected from hydride,dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonswith the proviso that in not more than one occurrence is Q halide.

[0216] In a more highly preferred embodiment, Q is a fluorinated C₁₋₂₀hydrocarbyl group, most preferably, a fluorinated aryl group,especially, pentafluorophenyl.

[0217] Illustrative, but not limiting, examples of ion forming compoundscomprising proton donatable cations which may be used as activatingcocatalysts in the preparation of the catalysts of this invention aretri-substituted ammonium salts such as:

[0218] trimethylammonium tetraphenylborate,

[0219] triethylammonium tetraphenylborate,

[0220] tripropylammonium tetraphenylborate,

[0221] tri(n-butyl)ammonium tetraphenylborate,

[0222] tri(t-butyl)ammonium tetraphenylborate,

[0223] N,N-dimethylanilinium tetraphenylborate,

[0224] N,N-diethylanilinium tetraphenylborate,

[0225] N,N-dimethyl(2,4,6-trimethylanilinium) tetraphenylborate,

[0226] trimethylammonium tetrakis-(penta-fluorophenyl) borate,

[0227] triethylammonium tetrakis-(pentafluorophenyl) borate,

[0228] tripropylammonium tetrakis(pentafluorophenyl) borate,

[0229] tri(n-butyl)-ammonium tetrakis(pentafluorophenyl) borate,

[0230] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0231] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[0232] N,N-diethylanilinium tetrakis(pentafluoro-phenyl) borate,

[0233] N,N-dimethyl(2,4,6-trimethyl-anilinium)tetrakis-(pentafluorophenyl) borate,

[0234] trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

[0235] triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

[0236] tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

[0237] tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

[0238] dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,

[0239] N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate,

[0240] N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate,and

[0241] N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate.

[0242] Dialkyl ammonium salts such as:

[0243] di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, and

[0244] dicyclohexylammonium tetrakis(pentafluorophenyl) borate.

[0245] Tri-substituted phosphonium salts such as: triphenylphosphoniumtetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphoniumtetrakis(penta-fluorophenyl) borate, andtri(2,6-dimethylphenyl)-phosphonium tetrakis(penta-fluorophenyl) borate.

[0246] Preferred are N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate and tributylammoniumtetrakis(pentafluorophenyl)borate.

[0247] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula:

(Ox^(e+))_(d) (A^(d−))_(e)

[0248] wherein:

[0249] Ox^(e+) is a cationic oxidizing agent having charge e+;

[0250] e is an integer from 1 to 3; and

[0251] A^(d−), and d are as previously defined.

[0252] Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

[0253] Another suitable ion forming, activating cocatalyst comprises acompound which is a salt of a carbenium ion or silylium ion and anoncoordinating, compatible anion represented by the formula:

{circle over (c)}⁺ A⁻

[0254] wherein:

[0255] {circle over (c)}⁺ is a C₁₋₂₀ carbenium ion or silylium ion; and

[0256] A⁻ is as previously defined.

[0257] A preferred carbenium ion is the trityl cation, that istriphenylcarbenium. A preferred silylium ion is triphenylsilylium.

[0258] The foregoing activating technique and ion forming cocatalystsare also preferably used in combination with a tri(hydrocarbyl)aluminumcompound having from 1 to 4 carbons in each hydrocarbyl group, anoligomeric or polymeric alumoxane compound, or a mixture of atri(hydrocarbyl)aluminum compound having from 1 to 4 carbons in eachhydrocarbyl group and a polymeric or oligomeric alumoxane.

[0259] An especially preferred activating cocatalyst comprises thecombination of a trialkyl aluminum compound having from 1 to 4 carbonsin each alkyl group and an ammonium salt oftetrakis(pentafluorophenyl)borate, in a molar ratio from 0.1:1 to 1:0.1,optionally up to 1000 mole percent of an alkylalumoxane with respect toM, is also present.

[0260] The activating technique of bulk electrolysis involves theelectrochemical oxidation of the metal complex under electrolysisconditions in the presence of a supporting electrolyte comprising anoncoordinating, inert anion. In the technique, solvents, supportingelectrolytes and electrolytic potentials for the electrolysis are usedsuch that electrolysis byproducts that would render the metal complexcatalytically inactive are not substantially formed during the reaction.More particularly, suitable solvents are materials that are: liquidsunder the conditions of the electrolysis (generally temperatures from 0°C. to 100° C.), capable of dissolving the supporting electrolyte, andinert. “Inert solvents” are those that are not reduced or oxidized underthe reaction conditions employed for the electrolysis. It is generallypossible in view of the desired electrolysis reaction to choose asolvent and a supporting electrolyte that are unaffected by theelectrical potential used for the desired electrolysis. Preferredsolvents include difluorobenzene (all isomers), DME, and mixturesthereof.

[0261] The electrolysis may be conducted in a standard electrolytic cellcontaining an anode and cathode (also referred to as the workingelectrode and counter electrode respectively). Suitable materials ofconstruction for the cell are glass, plastic, ceramic and glass coatedmetal. The electrodes are prepared from inert conductive materials, bywhich are meant conductive materials that are unaffected by the reactionmixture or reaction conditions. Platinum or palladium are preferredinert conductive materials. Normally, an ion permeable membrane such asa fine glass frit separates the cell into separate compartments, theworking electrode compartment and counter electrode compartment. Theworking electrode is immersed in a reaction medium comprising the metalcomplex to be activated, solvent, supporting electrolyte, and any othermaterials desired for moderating the electrolysis or stabilizing theresulting complex. The counter electrode is immersed in a mixture of thesolvent and supporting electrolyte. The desired voltage may bedetermined by theoretical calculations or experimentally by sweeping thecell using a reference electrode such as a silver electrode immersed inthe cell electrolyte. The background cell current, the current draw inthe absence of the desired electrolysis, is also determined. Theelectrolysis is completed when the current drops from the desired levelto the background level. In this manner, complete conversion of theinitial metal complex can be easily detected.

[0262] Suitable supporting electrolytes are salts comprising a cationand an inert, compatible, noncoordinating anion, A⁻. Preferredsupporting electrolytes are salts corresponding to the formula:

G⁺A⁻;

[0263] wherein:

[0264] G⁺ is a cation which is nonreactive towards the starting andresulting complex; and

[0265] A⁻ is a noncoordinating, compatible anion.

[0266] Examples of cations, G⁺, include tetrahydrocarbyl substitutedammonium or phosphonium cations having up to 40 nonhydrogen atoms. Apreferred cation is the tetra-n-butylammonium cation.

[0267] During activation of the complexes of the present invention bybulk electrolysis the cation of the supporting electrolyte passes to thecounter electrode and A⁻ migrates to the working electrode to become theanion of the resulting oxidized product. Either the solvent or thecation of the supporting electrolyte is reduced at the counter electrodein equal molar quantity with the amount of oxidized metal complex formedat the working electrode.

[0268] Preferred supporting electrolytes are tetrahydrocarbylammoniumsalts of tetrakis(perfluoroaryl) borates having from 1 to 10 carbons ineach hydrocarbyl group, especially tetra-n-butylammoniumtetrakis(pentafluorophenyl) borate.

[0269] The molar ratio of catalyst/cocatalyst employed preferably rangesfrom 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, mostpreferably from 1:10 to 10:1.

[0270] In general, the catalysts can be prepared by combining the twocomponents (metal complex and activator) in a suitable solvent at atemperature within the range from about ⁻100° C. to about 300° C. Thecatalyst may be separately prepared prior to use by combining therespective components or prepared in situ by combination in the presenceof the monomers to be polymerized.

[0271] It is understood with suitable functionality on the catalyst orcocatalyst the catalyst system can be covalently or ionically attachedto the support material.

[0272] Preferred supports for use in the present invention includehighly porous silicas, aluminas, aluminosilicates, and mixtures thereof.The most preferred support material is silica. The support material maybe in granular, agglomerated, pelletized, or any other physical form.Suitable materials include, but are not limited to, silicas availablefrom Grace Davison (division of W.R. Grace & Co.) under the designationsSD 3216.30, Davison Syloid 245, Davison 948 and Davison 952, and fromCrossfield under the designation ES70, and from Degussa AG under thedesignation Aerosil 812; and aluminas available from Akzo Chemicals Inc.under the designation Ketzen Grade B.

[0273] Supports suitable for the present invention preferably have asurface area as determined by nitrogen porosimetry using the B.E.T.method from 10 to about 1000 m²/g, and preferably from about 100 to 600m²/g. The pore volume of the support, as determined by nitrogenadsorption, advantageously is between 0.1 and 3 cm³/g, preferably fromabout 0.2 to 2 cm³/g. The average particle size depends upon the processemployed, but typically is from 0.5 to 500 μm, preferably from 1 to 100μm.

[0274] Both silica and alumina are known to inherently possess smallquantities of hydroxyl functionality. When used as a support herein,these materials are preferably subjected to a heat treatment and/orchemical treatment to reduce the hydroxyl content thereof. Typical heattreatments are carried out at a temperature from 30° C. to 1000° C.(preferably 250° C. to 800° C. for 5 hours or greater) for a duration of10 minutes to 50 hours in an inert atmosphere or under reduced pressure.Typical chemical treatments include contacting with Lewis acidalkylating agents such as trihydrocarbyl aluminum compounds,trihydrocarbylchlorosilane compounds, trihydrocarbylalkoxysilanecompounds or similar agents. Residual hydroxyl groups are then removedvia chemical treatment.

[0275] The support may be functionalized with a silane or chlorosilanefunctionalizing agent to attach thereto pendant silane —(Si—R)═, orchlorosilane —(Si—Cl)═ functionality, wherein R is a C₁₋₁₀ hydrocarbylgroup. Suitable functionalizing agents are compounds that react withsurface hydroxyl groups of the support or react with the silicon oraluminum of the matrix. Examples of suitable functionalizing agentsinclude phenylsilane, hexamethyldisilazane diphenylsilane,methylphenylsilane, dimethylsilane, diethylsilane, dichlorosilane, anddichlorodimethylsilane. Techniques for forming such functionalizedsilica or alumina compounds were previously disclosed in U.S. Pat. Nos.3,687,920 and 3,879,368, the teachings of which are herein incorporatedby reference.

[0276] The support may also be treated with an aluminum componentselected from an alumoxane or an aluminum compound of the formula AlR¹_(x′)R² _(y′), wherein R¹ independently each occurrence is hydride or R,R² is hydride, R or OR, x′ is 2 or 3, y′ is 0 or 1 and the sum of x′ andy′ is 3. Examples of suitable R¹ and R² groups include methyl, methoxy,ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (allisomers), butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy.Preferably, the aluminum component is selected from the group consistingof aluminoxanes and tri(C₁₋₄ hydrocarbyl)aluminum compounds. Mostpreferred aluminum components are aluminoxanes, trimethylaluminum,triethyl luminum, tri-isobutyl luminum, and mixtures thereof.

[0277] Alumoxanes (also referred to as aluminoxanes) are oligomeric orpolymeric aluminum oxy compounds containing chains of alternatingaluminum and oxygen atoms, whereby the aluminum carries a substituent,preferably an alkyl group. The structure of alumoxane is believed to berepresented by the following general formulae (—Al(R)—O)_(m′), for acyclic alumoxane, and R₂Al—O(—Al(R)—O)_(m′)—AlR₂, for a linear compound,wherein R is as previously defined, and m′ is an integer ranging from 1to about 50, preferably at least about 4. Alumoxanes are typically thereaction products of water and an aluminum alkyl, which in addition toan alkyl group may contain halide or alkoxide groups. Reacting severaldifferent aluminum alkyl compounds, such as for example trimethylaluminum and tri-isobutyl aluminum, with water yields so-called modifiedor mixed alumoxanes. Preferred alumoxanes are methylalumoxane andmethylalumoxane modified with minor amounts of C₂₋₄ alkyl groups,especially isobutyl. Alumoxanes generally contain minor to substantialamounts of starting aluminum alkyl compound.

[0278] Particular techniques for the preparation of alumoxane typecompounds by contacting an aluminum alkyl compound with an inorganicsalt containing water of crystallization are disclosed in U.S. Pat. No.4,542,119. In a particular preferred embodiment an aluminum alkylcompound is contacted with a regeneratable water-containing substancesuch as hydrated alumina, silica or other substance. This is disclosedin EP-A-338,044. Thus the alumoxane may be incorporated into the supportby reaction of a hydrated alumina or silica material, which hasoptionally been functionalized with silane, siloxane,hydrocarbyloxysilane, or chlorosilane groups, with a tri (C₁₋₁₀ alkyl)aluminum compound according to known techniques. For the teachingscontained therein the foregoing patents and publications, or therecorresponding equivalent United States applications, are herebyincorporated by reference.

[0279] The treatment of the support material in order to also includeoptional alumoxane or trialkylaluminum loadings involves contacting thesame before, after or simultaneously with addition of the complex oractivated catalyst hereunder with the alumoxane or trialkylaluminumcompound, especially triethylaluminum or triisobutylaluminum. Optionallythe mixture can also be heated under an inert atmosphere for a periodand at a temperature sufficient to fix the alumoxane, trialkylaluminumcompound, complex or catalyst system to the support. Optionally, thetreated support component containing alumoxane or the trialkylaluminumcompound may be subjected to one or more wash steps to remove alumoxaneor trialkylaluminum not fixed to the support.

[0280] Besides contacting the support with alumoxane the alumoxane maybe generated in situ by contacting an unhydrolyzed silica or alumina ora moistened silica or alumina with a trialkyl aluminum compoundoptionally in the presence of an inert diluent. Such a process is wellknown in the art, having been disclosed in EP-A-250,600; U.S. Pat. No.4,912,075; and U.S. Pat. No. 5,008,228; the teachings of which, or ofthe corresponding U.S. application, are hereby incorporated byreference. Suitable aliphatic hydrocarbon diluents include pentane,isopentane, hexane, heptane, octane, isooctane, nonane, isononane,decane, cyclohexane, methylcyclohexane and combinations of two or moreof such diluents. Suitable aromatic hydrocarbon diluents are benzene,toluene, xylene, and other alkyl or halogen substituted aromaticcompounds. Most preferably, the diluent is an aromatic hydrocarbon,especially toluene. After preparation in the foregoing manner theresidual hydroxyl content thereof is desirably reduced to a level lessthan 1.0 meq of OH per gram of support by any of the previouslydisclosed techniques.

[0281] The cocatalysts of the invention may also be used in combinationwith a tri(hydrocarbyl)aluminum compound having from 1 to 10 carbons ineach hydrocarbyl group, an oligomeric or polymeric alumoxane compound, adi(hydrocarbyl)(hydrocarbyloxy)aluminum compound having from 1 to 10carbons in each hydrocarbyl or hydrocarbyloxy group, or a mixture of theforegoing compounds, if desired. These aluminum compounds are usefullyemployed for their beneficial ability to scavenge impurities such asoxygen, water, and aldehydes from the polymerization mixture. Preferredaluminum compounds include C₂₋₆ trialkyl aluminum compounds, especiallythose wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl,isobutyl, pentyl, neopentyl, or isopentyl, and methylalumoxane, modifiedmethylalumoxane and diisobutylalumoxane. The molar ratio of aluminumcompound to metal complex is preferably from 1:10,000 to 1000:1, morepreferably from 1:5000 to 100:1, most preferably from 1:100 to 100:1.

[0282] The molar ratio of catalyst/cocatalyst employed ranges from1:1000 to 1:10, preferably ranges from 1:10 to 10:1, more preferablyfrom 1:5 to 1:1, most preferably from 1:1.2 to 1:1. Mixtures of theactivating cocatalysts of the present invention may also be employed ifdesired. In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻¹²:1 to 10⁻⁵:1.

[0283] Molecular weight control agents can be used in combination withthe present cocatalysts. Examples of such molecular weight controlagents include hydrogen, trialkyl aluminum compounds or other knownchain transfer agents. It is understood that the present invention isoperable in the absence of any component which has not been specificallydisclosed. The following examples are provided in order to furtherillustrate the invention and are not to be construed as limiting. Unlessstated to the contrary, all parts and percentages are expressed on aweight basis.

[0284] The catalysts, whether or not supported, in any of the processesof this invention, whether gas phase, solution, slurry, or any otherpolymerization process, may be used to polymerize addition polymerizablemonomers include ethylenically unsaturated monomers, acetyleniccompounds, conjugated or nonconjugated dienes, polyenes, and mixturesthereof. Preferred monomers include olefins, for examples α-olefinshaving from 2 to 100,000, preferably from 2 to 30, more preferably from2 to 8 carbon atoms and combinations of two or more of such α-olefins.

[0285] Particularly suitable α-olefins include, for example, ethylene,propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,1-tetradecene, 1-pentadecene, and C₁₆-C₃₀ α-olefins or combinationsthereof, as well as long chain vinyl terminated oligomeric or polymericreaction products formed during the polymerization. Preferably, theα-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene,1-octene, and combinations of ethylene and/or propene with one or moreof such other α-olefins. Other preferred monomers include styrene, halo-or alkyl substituted styrenes, tetrafluoroethylene, vinylcyclobutene,1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and1,7-octadiene. Mixtures of the above-mentioned monomers may also beemployed.

[0286] A preferred group of olefin comonomers for polymerizations whereethylene is the monomer includes propene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1,7-octadiene, 1,5-hexadiene, 1,4-pentadiene, 1,9-decadiene,ethylidenenorbornene, styrene, or a mixture thereof. For polymerizationswherein propene is the monomer, the preferred comonomers are the same asthat immediately previous, but with the inclusion of ethylene instead ofpropene.

[0287] Long chain macromolecular α-olefins can be vinyl terminatedpolymeric remnants formed in situ during continuous solutionpolymerization reactions. Under suitable processing conditions such longchain macromolecular units may be polymerized into the polymer productalong with ethylene and other short chain olefin monomers to give smallquantities of long chain branching in the resulting polymer.

[0288] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions. Suspension, solution, slurry, gas phase orhigh pressure, whether employed in batch or continuous form or otherprocess conditions, may be employed if desired. Examples of such wellknown polymerization processes are depicted in WO 88/02009, U.S. Pat.Nos. 5,084,534; 5,405,922; 4,588,790; 5,032,652; 4,543,399; 4,564,647;4,522,987, which are incorporated herein by reference; and elsewhere.Preferred polymerization temperatures are from 0-250° C. Preferredpolymerization pressures are from atmospheric to 3000 atmospheres.

[0289] Preferably, the processes of this invention are performed in asingle reactor, which may have a single reaction vessel or two or morevessels producing essentially the same polyolefin copolymer composition.Thus, the polymerization processes of this invention do not produceblends, or where more than one reaction vessel is used do not requireblending to produce essentially homogeneous polyolefin copolymercompositions.

[0290] In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10⁻¹:1,more preferably from 10⁻¹²:1 to 10⁻⁵:1.

[0291] Suitable solvents for polymerization via a solution process arenoncoordinating, inert liquids. Examples include straight andbranched-chain hydrocarbons such as isobutane, butane, pentane, hexane,heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbonssuch as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbonssuch as perfluorinated C₄₋₁₀ alkanes, and aromatic and alkyl-substitutedaromatic compounds such as benzene, toluene, and xylene. Suitablesolvents also include liquid olefins which may act as monomers orcomonomers including ethylene, propylene, 1-butene, butadiene,cyclopentene, 1-hexene, 1-heptene 3-methyl-1-pentene,4-methyl-1-pentene, 1,4-hexadiene, 1,7-octadiene, 1,9-decadiene,1-octene, 1-decene, styrene, divinylbenzene, ethylidenenorbornene,allylbenzene, vinyltoluene (including all isomers alone or inadmixture), 4-vinylcyclohexene, and vinylcyclohexane. Mixtures of theforegoing are also suitable.

[0292] One such polymerization process comprises: contacting, optionallyin a solvent, one or more α-olefins with a catalyst in one or morecontinuous stirred tank or tubular reactors. U.S. Pat. Nos. 5,272,236and 5,278,272 related to olefin polymerizations in solution and areincorporated herein by reference.

[0293] The process of the present invention can be employed to advantagein the gas phase copolymerization of olefins. Gas phase processes forthe polymerization of olefins, especially the homopolymerization andcopolymerization of ethylene and propylene, and the copolymerization ofethylene with higher α-olefins such as, for example, 1-butene, 1-hexene,4-methyl-1-pentene are well known in the art. Such processes are usedcommercially on a large scale for the manufacture of high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE) and polypropylene.

[0294] The gas phase process employed can be, for example, of the typewhich employs a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported above a perforated plate, the fluidisation grid, by a flow offluidisation gas.

[0295] The gas employed to fluidize the bed comprises the monomer ormonomers to be polymerized, and also serves as a heat exchange medium toremove the heat of reaction from the bed. The hot gases emerge from thetop of the reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means of a blower orcompressor and a one or more heat exchangers to strip the gas of theheat of polymerization.

[0296] A preferred method of cooling of the bed, in addition to thecooling provided by the cooled the recycle gas, is to feed a volatileliquid to the bed to provide an evaporative cooling effect. The volatileliquid employed in this case can be, for example, a volatile inertliquid, for example, a saturated hydrocarbon having about 3 to about 8,preferably 4 to 6, carbon atoms. In the case that the monomer orcomonomer itself is a volatile liquid, or can be condensed to providesuch a liquid, this can be suitably be fed to the bed to provide anevaporative cooling effect. Examples of olefin monomers which can beemployed in this manner are olefins containing about three to abouteight, preferably three to six carbon atoms. The volatile liquidevaporates in the hot fluidized bed to form gas which mixes with thefluidizing gas. If the volatile liquid is a monomer or comonomer, itwill undergo some polymerization in the bed. The evaporated liquid thenemerges from the reactor as part of the hot recycle gas, and enters thecompression/heat exchange part of the recycle loop. The recycle gas iscooled in the heat exchanger and, if the temperature to which the gas iscooled is below the dew point, liquid will precipitate from the gas.This liquid is desirably recycled continuously to the fluidized bed. Itis possible to recycle the precipitated liquid to the bed as liquiddroplets carried in the recycle gas stream. This type of process isdescribed, for example in EP 89691; U.S. Pat. No. 4,543,399; WO 94/25495and U.S. Pat. No. 5,352,749, which are hereby incorporated by reference.A particularly preferred method of recycling the liquid to the bed is toseparate the liquid from the recycle gas stream and to reinject thisliquid directly into the bed, preferably using a method which generatesfine droplets of the liquid within the bed. This type of process isdescribed in BP Chemicals' WO 94/28032, which is hereby incorporated byreference.

[0297] The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition of catalyst.Such catalyst can be supported on an inorganic or organic supportmaterial as described above. The catalyst can also be subjected to aprepolymerization step, for example, by polymerizing a small quantity ofolefin monomer in a liquid inert diluent, to provide a catalystcomposite comprising catalyst particles embedded in olefin polymerparticles.

[0298] The polymer is produced directly in the fluidized bed bycatalyzed copolymerization of the monomer and one or more comonomers onthe fluidized particles of catalyst, supported catalyst or prepolymerwithin the bed. Start-up of the polymerization reaction is achievedusing a bed of preformed polymer particles, which are preferably similarto the target polyolefin, and conditioning the bed by drying with inertgas or nitrogen prior to introducing the catalyst, the monomers and anyother gases which it is desired to have in the recycle gas stream, suchas a diluent gas, hydrogen chain transfer agent, or an inert condensablegas when operating in gas phase condensing mode. The produced polymer isdischarged continuously or discontinuously from the fluidized bed asdesired.

[0299] The gas phase processes suitable for the practice of thisinvention are preferably continuous processes which provide for thecontinuous supply of reactants to the reaction zone of the reactor andthe removal of products from the reaction zone of the reactor, therebyproviding a steady-state environment on the macro scale in the reactionzone of the reactor.

[0300] Typically, the fluidized bed of the gas phase process is operatedat temperatures greater than 50° C., preferably from about 60° C. toabout 110° C., more preferably from about 70° C. to about 110° C.

[0301] Typically the molar ratio of comonomer to monomer used in thepolymerization depends upon the desired density for the compositionbeing produced and is about 0.5 or less. Desirably, when producingmaterials with a density range of from about 0.91 to about 0.93 thecomonomer to monomer ratio is less than 0.2, preferably less than 0.05,even more preferably less than 0.02, and may even be less than 0.01.Typically, the ratio of hydrogen to monomer is less than about 0.5,preferably less than 0.2, more preferably less than 0.05, even morepreferably less than 0.02 and may even be less than 0.01.

[0302] The above-described ranges of process variables are appropriatefor the gas phase process of this invention and may be suitable forother processes adaptable to the practice of this invention.

[0303] A number of patents and patent applications describe gas phaseprocesses which are adaptable for use in the process of this invention,particularly, U.S. Pat. Nos. 4,588,790; 4,543,399; 5,352,749; 5,436,304;5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670;5,473,028; 5,106,804; and EP applications 659,773; 692,500; and PCTApplications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032; WO95/13305; WO 94/26793; and WO 95/07942 all of which are herebyincorporated herein by reference.

[0304] Desirably, the polyolefin copolymer composition of this inventioncontains in polymerized form from 0.01 to 99.99 mole percent ethylene asthe monomer and from 99.99 to 0.01 mole percent of one or more olefincomonomers. More desirably, the composition contains in polymerized formfrom 0.1 to 99.9 mole percent ethylene as the monomer and from 99.9 to0.1 mole percent of one or more olefin comonomers. Preferably, thecomposition contains in polymerized form from 50 to 99.9 mole percentethylene as the monomer and from 50 to 0.1 mole percent of one or moreolefin comonomers. A highly preferred embodiment is that where thecomposition contains in polymerized form from 96 to 99.9 mole percentethylene as the monomer and from 4 to 0.1 mole percent of one or moreolefin comonomers.

[0305] Generally, it is desirable that the density of the composition befrom about 0.87 to about 0.96, although it may be higher or lower thanthis range. More highly desirably, the density is from about 0.90 toabout 0.94, and preferably from 0.910 to about 0.925. The compositiondesirably has a melt index I₂ of from about 0.01 to about 150, and anI₂₁/I₂ which is equal to or greater than 24, and a Mw/Mn of from about2.0 to about 10.

[0306] A preferred polyolefin copolymer composition is that wherein thecomposition has an I₂₁/I₂ which is equal to or greater than 24 and aMw/Mn of from about 2.0 to about 3.5.

[0307] A preferred polyolefin copolymer composition is that wherein thecomposition has a short chain branching distribution that is multimodal,or wherein the composition has a molecular weight distribution that ismultimodal.

[0308] Another preferred polyolefin copolymer composition of is thatwherein the density of the composition is from about 0.910 to about0.925, the comonomer to monomer molar ratio is less than 0.02, thehydrogen to monomer ratio is less than 0.02, and the composition isproduced in a reactor with a reaction zone having a temperature of 70°C. or higher.

[0309] The homogeneity of the polymers is typically described by theSCBDI (Short Chain Branch Distribution Index) or CDBI (CompositionDistribution Branch Index) and is defined as the weight percent of thepolymer molecules having a comonomer content within 50 percent of themedian total molar comonomer content. The SCBDI of a polymer is readilycalculated from data obtained from techniques known in the art, such as,for example, temperature rising elution fractionation (abbreviatedherein as “TREF”) as described, for example, in Wild et al, Journal ofPolymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), in U.S. Pat.No. 4,798,081 (Hazlitt et al.), or in U.S. Pat. No. 5,089,321 (Chum etal.) the disclosures of all of which are incorporated herein byreference. The SCBDI or CDBI for the homogeneous linear and for thesubstantially linear ethylene/α-olefin polymers used in the presentinvention is preferably greater than 50 percent.

[0310] For the polyolefin polymer compositions of this invention, thelong chain branch is longer than the short chain branch that resultsfrom the incorporation of one or more α-olefin comonomers into thepolymer backbone. The empirical effect of the presence of long chainbranching in the copolymers of this invention is manifested as enhancedrheological properties which are indicated by higher flow activationenergies, and greater I₂₁/I₂ than expected from the other structuralproperties of the compositions.

[0311] Measurement of comonomer content vs log molecular weight byGPC/FTIR

[0312] The comonomer content as a function of molecular weight wasmeasured by coupling a Fourier transform infrared spectrometer (FTIR) toa Waters 150° C. Gel Permeation Chromatograph (GPC). The setting up,calibration and operation of this system together with the method fordata treatment has been described previously (L. J. Rose et al,“Characterisation of Polyethylene Copolymers by Coupled GPC/FTIR” in“Characterisation of Copolymers”, Rapra Technology, Shawbury UK, 1995,ISBN 1-85957-048-86.) In order to characterize the degree to which thecomonomer is concentrated in the high molecular weight part of thepolymer, the GPC/FTIR was used to calculate a parameter named comonomerpartition factor, Cpf. M_(n) and M_(w) were also determined usingstandard techniques from the GPC data.

[0313] Comonomer Partitioning Factor (GPC-FTIR)

[0314] The comonomer partitioning factor C_(pf) is calculated fromGPC/FTIR data. It characterizes the ratio of the average comonomercontent of the higher molecular weight fractions to the averagecomonomer content of the lower molecular weight fractions. Higher andlower molecular weight are defined as being above or below the medianmolecular weight respectively, that is, the molecular weightdistribution is divided into two parts of equal weight. C_(pf) iscalculated from the following equation:${C_{pf} = \frac{\frac{\frac{\sum\limits_{i = 1}^{n}\quad {w_{i}\quad c_{i}}}{\sum\limits_{i = 1}^{n}\quad w_{i}}}{\sum\limits_{j = 1}^{m}\quad {w_{j} \cdot c_{j}}}}{\sum\limits_{j = 1}^{m}\quad w_{j}}},$

[0315] where: c_(i) is the mole fraction comonomer content and w_(i) isthe normalized weight fraction as determined by GPC/FTIR for the n FTIRdata points above the median molecular weight. c_(j) is the molefraction comonomer content and w_(i) is the normalized weight fractionas determined by GPC/FTIR for the m FTIR data points below the medianmolecular weight. Only those weight fractions, w_(i) or w_(j) which haveassociated mole fraction comonomer content values are used to calculateC_(pf). For a valid calculation, it is required that n and m are greaterthan or equal to 3. FTIR data corresponding to molecular weightfractions below 5,000 are not included in the calculation due to theuncertainties present in such data.

[0316] For the polyolefin copolymer compositions of this invention,C_(pf) desirably is equal to or greater than 1.10, more desirably isequal to or greater than 1.15, even more desirably is equal to orgreater than 1.20, preferably is equal to or greater than 1.30, morepreferably is equal to or greater than 1.40, even more preferably isequal to or greater than 1.50, and still more preferably is equal to orgreater than 1.60.

[0317] ATREF-DV

[0318] ATREF-DV has been described in U.S. Pat. No. 4,798,081, which ishereby incorporated by reference, and in “Determination of Short-ChainBranching Distributions of Ethylene copolymers by Automated AnalyticalTemperature Rising Elution Fractionation” (Auto-ATREF), J. of Appl PolSci: Applied Polymer Symposium 45, 25-37 (1990). ATREF-DV is a dualdetector analytical system that is capable of fractionatingsemi-crystalline polymers like Linear Low Density Polyethylene (LLDPE)as a function of crystallization temperature while simultaneouslyestimating the molecular weight of the fractions. With regard to thefractionation, ATREF-DV is analogous to Temperature Rising ElutionFractionation (TREF) analysis that have been published in the openliterature over the past 15 years. The primary difference is that thisAnalytical-TREF (ATREF) technique is done on a small scale and fractionsare not actually isolated. Instead, a typical liquid chromatographic(LC) mass detector, such as an infrared single frequency detector, isused to quantify the crystallinity distribution as a function of elutiontemperature. This distribution can then be transformed to any number ofalternative domains such as short branching frequency, comonomerdistribution, or possibly density. Thus, this transformed distributioncan then be interpreted according to some structural variable likecomonomer content, although routine use of ATREF for comparisons ofvarious LLDPE's is often done directly in the elution temperaturedomain.

[0319] To obtain ATREF-DV data, a commercially available viscometerespecially adapted for LC analysis, such as a Viskotek™ is coupled withthe IR mass detector. Together these two LC detectors can be used tocalculate the intrinsic viscosity of the ATREF-DV eluant. The viscosityaverage molecular weight of a given fraction can then be estimated usingappropriate Mark Houwink constants, the corresponding intrinsicviscosity, and suitable coefficients to estimate the fractionsconcentration (dl/g) as it passes through the detectors. Thus, a typicalATREF-DV report will provide the weight fraction polymer and viscosityaverage molecular weight as a function of elution temperature. Mpf isthen calculated using the equation given.

[0320] Molecular Weight Partitioning Factor

[0321] The molecular weight partitioning factor M_(pf) is calculatedfrom TREF/DV data. It characterizes the ratio of the average molecularweight of the fractions with high comonomer content to the averagemolecular weight of the fractions with low comonomer content. Higher andlower comonomer content are defined as being below or above the medianelution temperature of the TREF concentration plot respectively, thatis, the TREF data is divided into two parts of equal weight. M_(pf) iscalculated from the following equation:${M_{pf} = \frac{\frac{\frac{\sum\limits_{i = 1}^{n}\quad {w_{i}\quad M_{i}}}{\sum\limits_{i = 1}^{n}\quad w_{i}}}{\sum\limits_{j = 1}^{m}\quad {w_{j}\quad M_{j}}}}{\sum\limits_{j = 1}^{m}\quad w_{j}}},$

[0322] where: M_(i) is the viscosity average molecular weight and w_(i)is the normalized weight fraction as determined by ATREF-DV for the ndata points in the fractions below the median elution temperature. M_(j)is the viscosity average molecular weight and w_(j) is the normalizedweight fraction as determined by ATREF-DV for the m data points in thefractions above the median elution temperature. Only those weightfractions, w_(i) or w_(j) which have associated viscosity averagemolecular weights greater than zero are used to calculate M_(pf). For avalid calculation, it is required that n and m are greater than or equalto 3.

[0323] For the polyolefin copolymer compositions of this invention,M_(pf) desirably is equal to or greater than 1.15, more desirably isequal to or greater than 1.30, even more desirably is equal to orgreater than 1.40, preferably is equal to or greater than 1.50, morepreferably is equal to or greater than 1.60, even more preferably isequal to or greater than 1.70.

[0324] Activation Energy as an Indicator of Long Chain Branching

[0325] The significance and determination of the activation energy offlow, which represents the temperature dependence of the viscosity, hasbeen described extensively (J. M. Dealy and K. F. Wissbrun, “MeltRheology and its Role in Plastics Processing”, Van Nostrand Reinhold,New York (1990)). For polyolefins, the Arrhenius equation is generallyused to describe the temperature dependence of viscosity since T>Tg+100(that is, the melt temperature (T) is greater than the glass transitiontemperature (Tg)+100; if this inequality is not true theWilliams-Landel-Ferry or WLF equation is used to describe thetemperature dependence of the viscosity). It has also been wellestablished that long chain branched polymers have higher activationenergies than comparable linear polymers. These comparisons have beenshown for homopolymer polyethylene, in which the activation energy forthe linear homopolymer is about 6.5 kcal/mol as compared to about 12 to14 kcal/mol for long chain branched polymers produced by the highpressure, free radical process. When using an activation energytechnique as an indicator of long chain branching, one must be carefulto take into account sources of extraneous effects such as crosslinking,comonomer content effects, or impurities such as cocatalyst residue.

[0326] For polyolefin copolymers, taking into account the effectsdescribed in the preceding paragraph, a value for the activation energyof about 8 kcal/mol or more in combination with greater I₂₁/I₂ thanexpected from the other structural properties of the compositions can beindicative of the presence of long chain branching, and especially avalue for the activation energy of about 10 kcal/mol or more, incombination with greater I₂₁/I₂ than expected from the other structuralproperties of the compositions, definitely indicates the presence oflong chain branching. The preferred polyolefin copolymer compositions ofone embodiment of this invention desirably have at least about 0.01 longchain branches per 1000 carbon atoms along the polymer backbone, moredesirably from about 0.01 to about 8 long chain branches per 1000 carbonatoms along the polymer backbone, preferably from about 0.01 to about 3long chain branches per 1000 carbon atoms along the polymer backbone,more preferably from about 0.01 to about 1 long chain branches per 1000carbon atoms along the polymer backbone, and still more preferably fromabout 0.02 to about 0.5 long chain branches per 1000 carbon atoms alongthe polymer backbone. It should be understood that, when long chainbranching is measured by some experimental techniques, such as NMR, theunits for the aforementioned ranges of values for the number of longchain branches are per 1000 total carbon atoms.

[0327] The temperature dependence of the viscosity for polyethylenes canbe expressed in terms of an Arrhenius equation, in which the activationenergy can be related to a shift factor, a_(T), used to determine amastercurve for the material by time-temperature superposition. Thevalues of the shift factor a_(T) are independent of molecular weight andmolecular weight distribution (W. W. Graessley, “Viscoelasticity andFlow in Polymer Melts and Concentrated Solutions”, in J. E. Mark et al.,Ed., “Physical Properties of Polymers”, 2^(nd) Ed., ACS, New York(1993); J. Wang and R. S. Porter, “On The Viscosity-Temperature Behaviorof Polymer Melts”, Rheol. Acta, 34, 496 (1995); R. S. Porter, J. P.Knox, and J. F. Johnson, “On the Flow and Activation Energy of BranchedPolyethylene Melts”, Trans. Soc. Rheol., 12, 409 (1968).), and thus theactivation energy is independent of molecular weight and molecularweight distribution for polymers that obey an Arrhenius relationshipbetween shift factors and inverse temperature. Others (V. R. Raju etal., “Properties of Amorphous and Crystallizable Hydrocarbon Polymers.IV. Melt Rheology of Linear and Star-Branched HydrogenatedPolybutadiene”, J. Polym. Sci., Polym. Phys. Ed., 17, 1223 (1979).) haveshown that the high activation energies (10-18 kcal/mol) of long chainbranched polybutadienes as compared to that of linear polyethylene (6.4kcal/mol) are related to long-chain branching. Variation of theactivation energy among long chain branched samples was concluded to bedue to variations in average branch lengths.

[0328] Determination of Activation Energy

[0329] Stabilization of Samples

[0330] If samples were received unstabilized, the samples werestabilized with the following stabilization package: 1250 ppm calciumstearate, 500 ppm Irganox 1076, and 800 ppm PEPQ. This stabilizationpackage was dissolved in acetone, which was then gently poured over thesample. The sample was then placed in a vacuum oven and dried at atemperature of 50-60° C. until the sample was dry (approximately oneday).

[0331] Molding of Samples

[0332] All samples were compression molded with a Tetrahedron MTP-8 HotPress before Theological testing. A tray was used to contain the samplesand to transfer the sample in and out of the press. A metal plate wasplaced on the tray, and a Mylar sheet was placed on top of the brassplate. The sample shims used were of approximately 2-3 mil thickness andslightly greater than 1 inch diameter in the form of a circle/disk.These shims were filled with sample, with up to 8 shims being used permolding. If many disks were required for a given sample, a 3 inchdiameter shim was used. Another piece of Mylar was then placed over thetop of the sample and over this was placed a metal plate. The tray withsamples was then placed between the tetrahedron plates, which were at350° F. The Tetrahedron plates are then brought together for 5 minuteswith a force of 1500 pounds. The tray was then removed from the pressand allowed to cool. An arc punch of 25 mm diameter was then used to cutthe samples for rheological testing.

[0333] Rheological Testing

[0334] Rheological testing was performed on a Rheometrics RMS-800 with25 mm diameter parallel plates in the dynamic mode. Before performingthe flow activation energy experiments, two strain sweep experimentswere performed to determine the percent strain to perform the activationenergy experiments so that the testing would be performed in the linearviscoelastic region and the torque signals would be significant. Onestrain sweep experiment was performed at the highest test temperature(210° C.) at a low frequency (0.1 rad/s) to determine the minimumpercent strain necessary to generate a significant torque signal. Thesecond strain sweep was performed at the lowest temperature (170° C.) atthe highest frequency (100 rad/s) to determine the maximum percentstrain allowable to remain within the linear viscoelastic region. Ingeneral, the percent strain ranged from 10-30 percent depending upon themolecular weight/stiffness of the sample.

[0335] The activation energies were determined by performing a frequencysweep from 100 to 0.01 rad/s with five points per decade at 210, 190,and 170° C. with a percent strain as determined above. A separate 25 mmdisk or plaque of material was used for each experiment. The Theologicaldata were analyzed with the Rheometrics RHIOS 4.4 software. Thefollowing conditions were selected for the time-temperaturesuperposition (t-T) and the determination of the flow activationenergies (Ea) according to an Arrhenius equation, a_(T)=exp(Ea/RT),which relates the shift factor (a_(T)) to E (R is the gas constant, andT is the absolute temperature):

[0336] Shift method: 2D

[0337] Shift accuracy: high

[0338] Interpolation: spline

[0339] all at 190° C. reference temperature.

[0340] The polyolefin copolymer compositions of a preferred embodimentof this invention desirably have a flow activation energy of at leastabout 8 kcal/mol, more desirably of at least about 10 kcal/mol,preferably of at least about 12 kcal/mol and more preferably of at leastabout 15 kcal/mol.

[0341] The polyolefin copolymer compositions of this invention may beblended with a wide variety of other resins to achieve a desirablebalance of physical properties, or for economic reasons. Generally, thephysical properties of the blends are what would be expected from aweighted interpolation of the physical properties of the individualcomponents, with the greatest deviations from linearity being seen whenone of the blend components is small relative to the other.

[0342] Desirably, the blends of this invention comprise two or moreresin components, (A) and (B), where the blend comprises from about 1weight percent to about 99 weight percent of (A) and from about 99weight percent to about 1 weight percent of one or more resins that aredifferent from the (A) component. The (A) component may be any of thepolyolefin copolymer compositions of this invention, while the (B)component may be any other resin which is not incompatible withcomponent (A). Preferred (B) components are various polyolefins.

[0343] In one embodiment, where it is desirable that the (B) componentpredominate, the blend comprises from about 1 weight percent to about 30weight percent of (A), and from about 99 weight percent to about 70weight percent of (B) one or more resins that are different from the (A)component. If a greater disparity in the amounts of the components isdesired, the blend comprises from about 1 weight percent to about 15weight percent of (A) and from about 99 weight percent to about 85weight percent of (B) one or more resins that are different from the (A)component.

[0344] In an alternative embodiment, where it is desirable that the (A)component predominate, the blend comprises from about 99 weight percentto about 70 weight percent of (A), and from about 1 weight percent toabout 30 weight percent of (B) one or more resins that are differentfrom the (A) component. If a greater disparity in the amounts of thecomponents is desired, the blend comprises from about 99 weight percentto about 85 weight percent of (A), and from about 1 weight percent toabout 15 weight percent of (B) one or more resins that are differentfrom the (A) component.

EXAMPLES

[0345] Examples 1-3 are three samples taken on three successive daysduring a single polymerization run. The same catalyst was usedthroughout the run and basically the same polymerization conditions weremaintained throughout the run.

[0346] Catalyst preparation for Examples 1-3

[0347] (i) Treatment of silica

[0348] 110 liters of hexane was placed in a 240 liter vessel undernitrogen and 0.75 g of Stadis™ 425 (diluted at 1 weight percent inhexane) was added. Stadis™ 425 is a hydrocarbon based antistatic agentavailable from DuPont Chemicals. 5 Kg of Sylopol™ 948 silica (previouslydried at 200° C. for 5 hours) was then added. 150 ml of water was thenadded at ambient temperature during a period of 1 hour. 16.67 moles ofTEA was then added at 30° C. during a period of 1 hour. After a holdingperiod of 30 minutes, the silica was washed 6 times with 130 liters ofhexane.

[0349] (ii) Catalyst fabrication

[0350] The silica treated as above was dried and then 25 liters oftoluene added. 59.59 liters of tris(pentafluorophenyl)boron solution inhexane (3.1 wt percent) was then added at ambient temperature during aperiod of 30 minutes. 3.38 liters of C₅Me₄SiMe₂NCMe₃TiMe₂((t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumdimethyl) solution in hexane (12.25 wt percent) was then added atambient temperature during a period of 15 minutes. The catalyst was thenheld at 25° C. for 1 hour, and a further 0.125 g of Stadis™ 425 added(diluted at 1 wt. percent in hexane). The catalyst was then dried at 40°C. under vacuum (20 mmHg) to give a free flowing powder with abrown/ochre color.

[0351] (iii) Polymerization using continuous fluidized bed reactor forExamples 1-3

[0352] Ethylene, n-hexene, hydrogen and nitrogen were fed into acontinuous fluidized bed reactor of diameter 45 cm. Polymer product wascontinuously removed from the reactor. Operating conditions andproperties of the composition are reported in Table 1. TABLE 1 ResinName Example 1 Example 2 Example 3 Example 4 Example 5 Example 6|(2.16), dg/min 1.36 0.85 0.91 0.86 1.20 0.77 |(21.6), dg/min 43.8 26.729.1 20.9 — — Density, g/cc .9230 .9158 .9120 .9178 .9200 .9153 Mw 8600095400 95100 — 120000 94592 Mw/Mn 2.68 2.63 2.19 3.4 6 3.43 Ea,kcal/mol13.15 11.07 10.31 7.39 19.2 — Cpf 1.34 1.24 1.26 1.22 1.12 1.67 Mpf 1.521.52 1.63 1.8 1.23 — DSC PEAK,C 119.86 117.99 117.9 — Temperature,C 8080 80 70 80 65 Comonomer 1-Hexene 1-Hexene 1-Hexene 1-Hexene 1-Hexene1-Hexene Catalyst Type mono-Cp mono-Cp mono-Cp mono-Cp bridged bisbridged bis Cp Cp Activator Borane Borane Borane Borane MAO MAO GasPhase Operating Conditions Total Press., Bar 16 16 16 9 20.2 20 Temp., C80.5 80 80.3 70 80 65 C2 Press., Bar 6.7 7.2 7.2 8 11 12 H2/C2 Press.0.003 0.0032 0.0033 0.0018 0.0011 0.005 C6/C2 Press 0.0034 0.0045 0.00480.0033 0.012 0.009 Production, kg/hr 10 10 15 11 —

Example 4

[0353] (i) Treatment of silica

[0354] A suspension of ES70 silica (7 kg, previously calcined at 500° C.for 5 hours) in 110 liters of hexane was made up in a 240 liter vesselunder nitrogen. A solution of TEA in hexane (9.1 moles, 0.976M solution)was added slowly to the stirred suspension over 30 minutes, whilemaintaining the temperature of the suspension at 30° C. The suspensionwas stirred for a further 2 hours. The hexane was filtered, and thesilica washed 4 times with hexane, so that the aluminum content in thefinal washing was less than 1 mmol Al/liter. Finally the suspension wasdried in vacuo at 40° C. to give a free flowing treated silica powder.

[0355] (ii) Catalyst fabrication

[0356] Na-dried, distilled toluene (55 ml) was added to 13 g of thetreated silica powder in a 250 ml round bottomed flask in a dry nitrogenglove box. To the suspension was added a solution oftris(pentafluorophenyl)boron in toluene (7.6 ml, 7.85 wt percent, d=0.88g/ml) by syringe. Then a solution of(t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumη⁴-1,3-pentadiene in toluene (2.6 ml, 10.7 wt percent, d=0.88 g/ml) wasadded by syringe. The suspension was shaken well for 5 minutes, thendried in vacuo at 20° C. to give a free-flowing pale green powder.

[0357] (iii) Polymerization using a semi-continuous fluidized bedreactor

[0358] Ethylene, n-hexene, hydrogen and nitrogen were fed into a batchfluidized bed reactor of diameter 15 cm. Starting with a seed bed ofLLDPE powder (˜1 Kg), catalyst was injected and polymerization carriedout to increase the mass of the bed to approximately 3.5 Kg. Product wasthen withdrawn to leave approximately 1 Kg of the powder in the reactor.The steps of polymerization and product withdrawal were carried out 5times in total to yield a product containing in the region of only 0.3percent by weight of the starting bed. The product was a white freeflowing powder of bulk density 0.36 g/cm³. The average productivity ofthe catalyst was about 1000 g polymer/g catalyst. Operating conditionsand properties of the composition are given in Table 1. Total pressure 9bar Temperature 70° C. Pressure C2 8 bar Pressure H2/C2 0.0018 PressureC6/C2 0.0033

Example 4A

[0359] (i) Treatment of silica

[0360] A suspension of ES70 silica (7 kg, previously calcined at 500° C.for 5 hours) in 110 liters of hexane was made up in a 240 liter vesselunder nitrogen. A solution of TEA in hexane (9.1 moles, 0.976M solution)was added slowly to the stirred suspension over 30 minutes, whilemaintaining the temperature of the suspension at 30° C. The suspensionwas stirred for a further 2 hours. The hexane was filtered, and thesilica washed 4 times with hexane, so that the aluminum content in thefinal washing was less than 1 mmol Al/liter. Finally the suspension wasdried in vacuo at 40° C. to give a free flowing treated silica powder.

[0361] (ii) Catalyst fabrication

[0362] Na-dried, distilled toluene (55 ml) was added to 13 g of thetreated silica powder in a 250 ml round bottomed flask in a dry nitrogenglove box. To the suspension was added a solution oftris(pentafluorophenyl)boron in toluene (7.6 ml, 7.85 wt percent, d=0.88g/ml) by syringe. Then a solution of(t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitaniumη⁴-3-methyl-1,3-pentadiene in toluene (2.6 ml, 10.7 wt percent, d=0.88g/ml) was added by syringe. The suspension was shaken well for 5minutes, then dried in vacuo at 20° C. to give a free-flowing pale greenpowder.

[0363] (iii) Polymerization using a semi-continuous fluidized bedreactor

[0364] Ethylene, n-hexene, hydrogen and nitrogen were fed into a batchfluidized bed reactor of diameter 15 cm. Starting with a seed bed ofLLDPE powder (˜1 Kg), catalyst was injected and polymerization carriedout to increase the mass of the bed to approximately 3.5 Kg. Product wasthen withdrawn to leave approximately 1 Kg of the powder in the reactor.The steps of polymerization and product withdrawal were carried out 5times in total to yield a product containing in the region of only 0.3percent by weight of the starting bed. The product was a white freeflowing powder of bulk density 0.36 g/cm³. The average productivity ofthe catalyst was about 1000 g polymer/g catalyst. Operating conditionsand properties of the composition are given in Table 1. Total pressure 9bar Temperature 70° C. Pressure C2 8 bar Pressure H2/C2 0.0018 PressureC6/C2 0.0033

Example 5

[0365] Catalyst preparation

[0366] The catalyst was prepared in an inert atmosphere vessel of volume110 liters maintained under an inert atmosphere. Mixing was appliedthroughout using a paddle stirrer operated at 20 rev/min. 7.5 moles ofMAO (1.6 mole/liter in toluene) were added at ambient temperature. Afurther 3.88 liters of toluene was added to rinse the addition system.100 mM of ethylene-bridged bis(indenyl) zirconium dichloride diluted in2.3 liters of toluene was then added and a further 1 liter of toluenefor rinsing. The temperature was raised to 80° C. and maintained at thisvalue for 1 hour, and then cooled to 50° C. and 2 Kg of ES70 silica(dried for 5 hours at 800° C.) was added. The temperature was raised to80° C. and maintained for 2 hours 0.5 g of Stadis™ 425 antistatic agentin 0.51 of toluene was then added and the catalyst dried at 70° C. undervacuum (700 torr).

[0367] Polymerization using continuous fluidized bed reactor for Example5

[0368] Ethylene, n-hexene, hydrogen and nitrogen were fed into acontinuous fluidized bed reactor of diameter 45 cm. Polymer product wascontinuously removed from the reactor through a valve. Operatingconditions are as follows: Total pressure 20.2 bar Temperature 80° C.Pressure C2 11 bar Pressure H2/C2 0.0011 Pressure C6/C2 0.012

[0369] The properties of the composition are given in Table 1. The valueof activation energy found by flow activation analysis was 19.2kcal/mol, which indicates significant long chain branching.

Example 6

[0370] Catalyst preparation

[0371] The catalyst was prepared in an inert atmosphere vessel of volume110 liters maintained under an inert atmosphere. Mixing was appliedthroughout using a paddle stirrer operated at 20 rev/min. 48.8 moles ofMAO (1.85 mole/liter in toluene) were added at ambient temperature. Afurther 3.88 liters of toluene was added to rinse the addition system.650 mM of ethylene-bridged bis(indenyl) zirconium dichloride diluted in5 liters of toluene was then added and a further 1.2 liter of toluenefor rinsing. The temperature was raised to 80° C. and maintained at thisvalue for 1 hour, and then cooled to 50° C. and 13 kg of ES70 silica(dried for 5 hours at 800° C.) was added.

[0372] The temperature was raised to 80° C. and maintained for 2 hours0.5 g of Stadis™ 425 antistatic agent in 0.11 of toluene was then addedand the catalyst dried at 70° C. under vacuum (700 mmHg).

[0373] Polymerization using continuous fluidized bed reactor for Example5

[0374] Ethylene, n-hexene, hydrogen and nitrogen were fed into acontinuous fluidized bed reactor of diameter 74 cm. Polymer product wascontinuously removed from the reactor through a valve. Operatingconditions are as follows: Total pressure 20.2 bar Temperature 65° C.Pressure C2 12 bar Pressure H2/C2 0.005 Pressure C6/C2 0.009

[0375] The properties of the composition are given in Table 1.

Examples 100-104

[0376] The same catalyst formula and preparation method as for Examples1-3 was used for preparation of the catalyst for these examples.However, only 3.5 Kg of silica was used and the quantities of all othercomponents were scaled down accordingly. Polymerization was carried outin the same continuous fluidized bed reactor of diameter 45 cm.Operating conditions and properties of the composition are reported inTable 1A.

[0377] In the Tables that follow I₂ and I₂ were determined by ASTMD-1238 and density by ASTM D-1505. TABLE 1A Example Example ExampleExample Example Example Example Example 100 101 102 103 104 105 106 107|(2.16), dg/min 0.85 0.84 3.70 3.00 2.00 0.96 1.41 0.96 |(21.6), dg/min27 25.6 94 78 57 21.7 .44 24.5 Density, g/cc .9170 .9160 .9202 .9200.9178 .9161 .9190 .9195 Mw Mw/Mn Ea, kcal/mol 13.4 14.7 8.9 7.8 10.27.66 13.3 11.1 Cpf 1.4 1.27 144 1.4 1.31 1.38 1.32 1.3 Mpf 1.89 1.521.81 1.84 1 68 1.54 1.52 DSC PEAK, C 1.54 1.52 Temperature,C 75 80 75 7575 71 75 74 Comonomer C6 C6 C6 C6 C6 C6 C6 C6 Catalyst Type mono-Cpmono-Cp mono-Cp mono-Cp mono-Cp mono-Cp mono-Cp mono-Cp Activator BoraneBorane Borane Borane Borane Borane Borane Borane Gas Phase OperatingConditions Total Press., Bar 16 16 16 16 16 18 16 16 Temp.,C 75 80 75 7575 71 75 74 C2 Press., Bar 7.4 7.4 9 9.7 9.7 8.7 6.3 7.6 H2/C2 Press.0.0035 0.004 0.0048 0.0042 0.0039 0.0019 0.0025 0.0032 C6/C2 Press0.0032 0.0032 0.0032 0.0034 0.0035 0.0039 0.0036 0.0038 Production,kg/hr 14 12 9 13 12 8 65 50

[0378] Catalyst Preparation for Example 105

[0379] (i) Treatment of silica

[0380] 110 liters of hexane was placed in a 240 liter vessel undernitrogen and 0.75 g of Stadis 425, diluted at 1 wt % in hexane, wasadded. 2.9 Kg of Crossfield ES70 silica, which had previously been driedat 500° C. for 5 hours, and which contained 1.1 mM OH/g) was then added.3.75 moles of TEA was then added at 30° C. during a period of 1 hour.After a holding period of 30 minutes, the silica was washed with hexaneto eliminate excess TEA and to reach the targeted aluminum in thesupernatent of 1 mM per liter of hexane.

[0381] (ii) Catalyst fabrication

[0382] The silica treated as above was dried and then 10.4 liters oftoluene added. 0.2 moles of tris(pentafluorophenyl)boron solution intoluene (7.85 wt %) was then added at ambient temperature during aperiod of 30 minutes. 0.15 moles of(t-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium-η⁴-1,3-pentadienein toluene (10.17 wt %) was then added at ambient temperature during aperiod of 15 minutes. A further 0.125 g of Stadis 425 was added (dilutedat 1 wt % in hexane). The catalyst was then dried at 40° C. under vacuum(20 mmHg) to give a free flowing powder with a green color.

[0383] (iii) Polymerization using continuous fluidized bed reactor forexamples 105

[0384] Ethylene, n-hexene, hydrogen and nitrogen were fed into acontinuous fluidized bed reactor of diameter 45 cm. Polymer product wascontinuously removed from the reactor. Operating conditions are given inTable 1A.

Example 106

[0385] The same catalyst formula and preparation method as for Examples1-3 was used for preparation of the catalyst for example 106. However,10 Kg of silica was used and the quantities of all other components werescaled up accordingly. Polymerization was carried out in a continuousfluidized bed reactor of diameter 74 cm. Operating conditions andproperties of the composition are reported in Table 1A.

Example 107

[0386] The same catalyst formula and preparation method as for Example105 was used for preparation of the catalyst for Example 107. However,17 Kg of silica was used and the quantities of all other components werescaled up accordingly. Polymerization was carried out in a continuousfluidized bed reactor of diameter 74 cm. Operating conditions andproperties of the composition are reported in Table 1A.

Comparative Examples A-F

[0387] Comparative Examples A-F are commercially available materialswhich were tested and compared under the same conditions to thecompositions of Examples 1-6. The data for the comparatives are in Table2. TABLE 2 Comparative A Comparative B Comparative C Comparative DComparative E Comparative F Resin Name INNOVEX 7209 EXCEED 401 NovapolTD9022 DOWLEX 2056A AFFINITY FM Enhanced PE AA 1570 |(2.16), dg/min 0.904.50 0.87 1.00 1.00 0.85 |(21.6), dg/min — — — — — Density, g/cc .9200.9170 .9170 .9200 0.915 .9200 Mw — 124200 113100 74700 118700 Mw/Mn 2.32.9 4.03 2.24 3.363 Ea, kcal/mol 6.82 8.47 (see pg 49) — 7.28 14.1 Cpf<1 — <1 — 1.06 — Mpf 0.45 1.11 0.61 0.62 0.73 2.32 DSC PEAK,C 116 124122 Temperature,C — — — 195 — — Comonomer 4-methyl-1- 1-Hexene 1-Hexene1-Octene 1-Octene 1-Octene pentene Catalyst Type Traditional bis-CpTraditional Traditional mono-Cp Ziegler-Natta Ziegler-NattaZiegler-Natta Promoter Type Gas Phase Operating Conditions — — — — TotalPress., Bar — — — — Temp., C — — — — C2 Press., Bar — — — — H2/C2 Press,— — — — C6/C2 Press — — — — Production, kg/hr

[0388] Comparative A is Innovex™ 7209, a commercially available gasphase produced polyethylene produced by BP Chemicals using a traditionalZiegler-Natta catalyst.

[0389] Comparative B is Exxon Exceed™ 401, a commercially available gasphase produced polyethylene produced by Exxon Chemical using ametallocene catalyst. (Note: A second sample of this material wasevaluated, and a value for E_(a) of 7.53 kcal/mol was determined, aswell as a value for I₂₁ of 77.92 and I₁₀ of 27.02, and, thus, a value ofI₂₁/I₂ of 17.3 and I₁₀/I₂ of 6.0. In addition, the critical shear rateat the onset of surface melt fracture was 294 s⁻¹ at a shear stress of2.15×10⁶ dyn/cm² and the critical shear rate at the onset of gross meltfracture was 795 s⁻¹ at a shear stress of 3.45×10⁶ dyn/cm². This dataindicates the absence of long chain branching.)

[0390] Comparative C is Novapol™ TD902, a commercially available gasphase produced polyethylene produced by Novascor™ using a traditionalZiegler-Natta catalyst.

[0391] Comparative D is DOWLEX™ 2056A, a commercially available solutionprocess polyethylene produced by The Dow Chemical Company using atraditional Ziegler-Natta catalyst.

[0392] Comparative E is AFFINITY™ FM 1570, a commercially availablesolution process polyethylene produced by The Dow Chemical Company usinga constrained geometry metallocene catalyst.

[0393] Comparative F is enhanced polyethylene XU-59900.00, acommercially available solution process polyethylene produced by The DowChemical Company.

[0394] The improved processability observed for the compositions ofExamples 2a (see note 5 below) and 3 are due to the presence of longchain branching in the polymer. DOWLEX™ 2056A, produced by the solutionprocess using Ziegler-Natta catalyst, contains no long chain branching.The presence of long chain branching results in higher melt strengthwhich was measured by a Goettfert Rheotens apparatus. The data isreported in Table 3. TABLE 3 DOWLEX ™ 2056A EX 2a EX 3 Resin PropertiesMelt Index, dg/min. 1.0 1.1 0.91 Density, g/cc 0.920 0.915 0.912Processability¹ Motor Current, amp. 65 53 56 Pressure, psig 2690 26102770 Screw Power, hp 15 13 12 Bubble Stability² Melt Strength, cN 4 9 7Sealing Properties³ Seal Strength, lb. 4.2 4.6 4.7 Hot Tack, lb. 0.4 2.72.8 Film Toughness⁴ Dart Impact Strength, g 86 850 850

[0395] The polyolefin copolymer compositions of this invention havemechanical properties, such as dart impact strength, optical propertiesand heat sealing properties which are superior to conventional Zieglerproduced compositions of comparable density. They also haveprocessability characteristics, as measured, for example, by meltstrength and melt flow ratio, which are superior to conventionalmetallocene products of comparable density and melt index, and inespecially preferred embodiments, to conventional Ziegler materials aswell. The polyolefin copolymer compositions also offer the advantagethat they can be manufactured using a single catalyst in a singlereactor process. In the preferred embodiment, the materials of theinvention can be extruded through conventional polyethylene extruderswith lower power requirements, lower extruder pressures, and lower melttemperatures then conventional Ziegler-Natta and conventionalmetallocene products.

[0396] Films and other articles of manufacture produced with thepolyolefin copolymer compositions of this invention desirably have amelt strength of greater than 4 CNN, preferably equal to or greater than7, more preferably equal to or greater than 9. The seal strengthdesirably is greater than 4.2 lb., preferably equal to or greater than4.6 lb., more preferably equal to or greater than 4.8 lb. The hot tackis desirably is greater than 0.5 lb., preferably equal to or greaterthan 1.0 lb., more preferably equal to or greater than 2.0 lb. The dartimpact strength desirably is greater than 100 g, more desirably greaterthan 200 g, preferably equal to or greater than 500 g, more preferablyequal to or greater than 700, and even more preferably equal to orgreater than 850 g.

[0397] Blends of the polyolefin copolymer composition with ethylenehomopolymer

[0398] Blends of the polyolefin copolymer composition of this inventionwith an ethylene homopolymer produced by a high pressure tubular processhave been prepared and studied. Polyolefin copolymer compositionsdesignated by L022, from Example 100, and L023, from Example 101, wereindividually blended with an ethylene homopolymer resin (LDPE 501I) atlevels between 0 and 100 per cent. None of these resins contained slipor antiblock additives, except the LDPE 501I, which was stabilized with500 ppm Irganox 1076, a phenolic antioxidant. Characteristics of theresins used for the blends is reported in Table 4. TABLE 4 ResinProperties Resin Melt Index Density Description L022 0.89 0.9161 GasPhase-Substantially linear ethylene polymer, INSITE ™ Catalyst L023 0.850.9177 Gas Phase-Substantially linear ethylene polymer, INSITE ™Catalyst 501I 1.90 0.9220 Ethylene Homopolymer, High pressure Tubularprocess

[0399] Data related to the composition of these blends and the unblendedmaterials are presented for Samples A through G in Table 5. TABLE 5Blend Composition Weight % Resin Sample L022 L023 LDPE A 100 0 0 B 90 010 C 20 0 80 D 0 0 100 E 0 100 0 F 0 95 5 G 0 20 80

[0400] Blending LDPE into the substantially linear low density polymerof this invention gave improvements in processability relative to theunblended polyolefin copolymer composition of this invention due to theincrease in amounts of long chain branching, and as demonstrated by areduction in extruder amps and pressure. Data related to processabilityare shown in Table 6. The blends also provide significant improvementsin optical characteristics, as shown by a reduction in haze and anincrease in both clarity and gloss relative to the unblended polyolefincopolymer composition of this invention, which is evident from the datain Table 7. TABLE 6 Processability Extruder Conditions Sample rpm lb/hrMelt Temp amp psi A 57.2 120 442 51 2260 B 57.6 120 442 55 2440 C 54 120438 36 1310 D 58.6 120 434 34 990 E 58.9 117 442 54 2510 F 58.6 119 44255 2570 G 53.8 120 438 37 1450

[0401] TABLE 7 Optical Characteristics Gloss Gloss Sample Clarity 20deg. 45 deg. A 91.6 44.1 61.1 B 92.9 59.2 66.7 C 93.1 57.5 71.5 D 95.574.1 76.1 E 90.2 49.5 62.2 F 92.2 59.3 66 G 92.5 54.4 69.6

[0402] For films made with the blends there was a noted improvement inheat seal initiation temperature, as indicated by a reduction intemperature required to obtain a 2 pound Heat Seal, and in the finalSeal Strength in pounds, relative to the unblended polyolefin copolymercomposition of this invention. Data related to this aspect of Heat Sealand Seal Strength are presented in Table 8. TABLE 8 Heat Seal/SealStrength Heat Seal % LDPE Initiation Temp. Seal Strength, lb. 0 109 C.2.1 10 108 C. 2.2 80 104 C. 2.9 100 102 C. 2.7

[0403] As levels of the homopolymer LDPE resin were increased, anaccompanying decrease in film strength, or mechanical properties,relative to the unblended polyolefin copolymer composition of thisinvention, was observed as the linear nature of the blend was decreased.Reductions in the mechanical properties are shown in Table 10 below.

[0404] Blending the polyolefin copolymer composition of this inventioninto a LDPE homopolymer gave improvements in the resulting film physicalproperties such as Ultimate Tensile Strength, Dart Impact Resistance,Elmendorf Tear, and Hot Tack Strength, relative to the unblended LDPE.

[0405] Hot Tack Strength is the strength, in Newtons, required to pullapart two films in a partially molten condition. This test is used tosimulate the ability of a package to hold its seal, and not spill thecontents, while the heat seal has not yet cooled. As the polyolefincopolymer composition of this invention was blended into the LDPE, thehot tack strength increased as did the temperature range in which thehot tack was observed. The data are presented in Table 9. TABLE 9 HotTack % LDPE Hot Tack Strength, N Temperature Range, C. 0 3.4 35 10 3.425 80 1.8 15 100 1.6 10

[0406] MD Elmendorf tear, being relatively low for the polyolefincopolymer compositions of this invention, was relatively unaffected bythe addition of LDPE. The orientation effect did vary the CD tear. Thedart impact for the polyolefin copolymer compositions of this inventionis quite high, and only slightly affected at moderate levels of blendingwith LDPE. Data for these film physical properties are given in Table10. TABLE 10 Film Physical Properties Description Elmendorf Tear DartImpact Sample L022 L023 LDPE MD CD grams A 100 0 0 187 317 658 B 90 0 10186 613 654 C 20 0 80 162 256 100 D 0 0 100 152 238 100 E 0 100 0 168646 508 F 0 95 5 155 726 556 G 0 20 80 166 650 100

[0407] Thus, it is clear that, while the high strength of the polyolefincopolymer compositions of this invention were compromised to some degreeby blending with an LDPE homopolymer, other properties may beadvantageously affected. Similarly, while some properties of anunblended LDPE homopolymer may be adversely affected by blending withthe polyolefin copolymer composition of this invention, the strength ofthe blend is superior to unblended LDPE.

1. A polyolefin copolymer composition produced with a catalyst having ametallocene complex in a single reactor in a process for thepolymerization of an α-olefin monomer with one or more olefincomonomers, the composition having a molecular weight maximum whichoccurs in that 50 percent by weight of the composition which has thehighest weight percent comonomer content, as expressed by having aconomoner partitioning factor C_(pf) which is equal to or greater than1.10 and/or a molecular weight partitioning factor M_(pf) which is equalto or greater than 1.15, where the comonomer partitioning factor C_(pf)is calculated from the equation:$C_{pf} = \frac{\left( \frac{\sum\limits_{i = 1}^{n}\quad {w_{i}\quad c_{i}}}{\sum\limits_{i = 1}^{n}\quad w_{i}} \right)}{\left( \frac{\sum\limits_{j = 1}^{m}\quad {w_{j}c_{j}}}{\sum\limits_{j = 1}^{m}\quad w_{j}} \right)}$

where c_(l) is the mole fraction comonomer content and w_(i) is thenormalized weight fraction as determined by GPC/FTIR for the n FTIR datapoints above the median molecular weight, c_(j) is the mole fractioncomonomer content and w_(j) is the normalized weight fraction asdetermined by PGC/FTIR for the m FTIR data points below the medianmolecular weight, wherein only those weight fractions w₁ or w_(j) whichhave associated mole fraction comonomer content values are used tocalculate C_(pf) and n and m are greater than or equal to 3; and wherethe molecular weight partitioning factor M_(pf) is calculated from theequation:$M_{pf} = \frac{\left( \frac{\sum\limits_{i = 1}^{n}\quad {w_{i}\quad M_{i}}}{\sum\limits_{i = 1}^{n}\quad w_{i}} \right)}{\left( \frac{\sum\limits_{j = 1}^{m}\quad {w_{j}M_{j}}}{\sum\limits_{j = 1}^{m}\quad w_{j}} \right)}$

where M_(i) is the viscosity average molecular weight and w_(l) is thenormalized weight fraction as determined by ATREF-DV for the n datapoints in the fractions below the median elution temperature. M_(j) isthe viscosity average molecular weight and w_(j) is the normalizedweight fraction as determined by ATREF-DV for the m data points in thefractions above the median elution temperature, wherein only thoseweight fractions, w_(i) or w_(j) which have associated viscosity averagemolecular weights greater than zero are used to calculated M_(pf) and nand m are greater than or equal to
 3. 2. The polyolefin composition ofclaim 1, having long chain branches along the polymer backbone.
 3. Thepolyolefin copolymer composition of claim 1 or 2, wherein C_(pf) isequal to or greater than 1.15.
 4. The polyolefin copolymer compositionof claim 3 wherein C_(pf) is equal to or greater than 1.20.
 5. Thepolyolefin copolymer composition of claim 2 wherein M_(pf) is equal toor greater than 1.30.
 6. The polyolefin copolymer composition of claim 5wherein M_(pf) is equal to or greater than 1.50.
 7. The polyolefincopolymer composition of claim 1 wherein the density of the compositionis from 0.87 to 0.96 g/cm³.
 8. The polyolefin copolymer composition ofclaim 7 wherein the density of the composition is from 0.90 to 0.94g/cm³.
 9. The polyolefin copolymer composition of claim 8 wherein thedensity of the composition is from 0.910 to 0.925 g/cm³.
 10. Thepolyolefin copolymer composition of claim 1 wherein the composition hasa melt index I₂ of from 0.01 to
 150. 11. The polyolefin copolymercomposition of claim 1 wherein the composition has an I₂₁/I₂ which isequal to or greater than
 24. 12. The polyolefin copolymer composition ofclaim 1 wherein the composition has a Mw/Mn of from 2.0 to
 10. 13. Thepolyolefin copolymer composition of claim 1 wherein the composition hasan I₂₁/I₂ which is equal to or greater than 24 and a Mw/Mn of from 2.0to3.5.
 14. The polyolefin copolymer composition of claim 1 wherein thecomposition has a flow activation energy of at least 8 kcal/mol.
 15. Thepolyolefin copolymer composition of claim 14 wherein the composition hasa flow activation energy of at least 10 kcal/mol.
 16. The polyolefincopolymer composition of claim 15 wherein the composition has a flowactivation energy of at least 12 kcal/mol.
 17. The polyolefin copolymercomposition of claim 2 wherein the composition has at least 0.01 longchain branches per 1000 carbon atoms along the polymer backbone.
 18. Thepolyolefin copolymer composition of claim 17 wherein the composition hasfrom 0.01 to 8 long chain branches per 1000 carbon atoms along thepolymer backbone.
 19. The polyolefin copolymer composition of claim 18wherein the composition has from 0.01 to 3 long chain branches per 1000carbon atoms along the polymer backbone.
 20. The polyolefin copolymercomposition of claim 1 wherein the olefin comonomer is propene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1,7-octadiene, 1,5-hexadiene, 1,4-pentadiene,1,9-decadiene, ethylidenenorbornene, styrene or a mixture thereof. 21.The polyolefin copolymer composition of claim 1 wherein the compositioncontains in polymerized form from 0.01 to 99.99 mole percent ethylene asthe monomer and from 99.99 to 0.01 mole percent of one or more olefincomonomers.
 22. The polyolefin copolymer composition of claim 21 whereinthe composition contains in polymerized form from 0.1 to 99.99 molepercent ethylene as the monomer and from 99.99 to 0.1 mole percent ofone or more olefin comonomers.
 23. The polyolefin copolymer compositionof claim 22 wherein the composition contains in polymerized form from 50to 99.99 mole percent ethylene as the monomer and from 50 to 0.1 molepercent of one or more olefin comonomers.
 24. The polyolefin copolymercomposition of claim 23 wherein the composition contains in polymerizedform from 96 to 99.9 mole percent ethylene as the monomer and from 4 to0.1 mole percent of one or more olefin comonomers.
 25. The polyolefincopolymer composition of claim 1 wherein the composition contains inpolymerized form from 0.01 to 99.99 weight percent propylene as themonomer and from 99.99 to 0.01 weight percent of one or more olefincomonomers.
 26. The polyolefin copolymer composition of claim 1 whereinthe composition has been produced with a mono-Cp catalyst.
 27. Thepolyolefin copolymer composition of claim 26 wherein the metallocenecomplex of the catalyst has a central metal Ti in which the formaloxidation state is +2.
 28. The polyolefin copolymer composition of claim27 wherein the composition has been produced with a catalyst having ametallocene complex of the formula:

wherein M is titanium or a zirconium in the +2 formal oxidation state; Lis a group containing a cyclic, delocalized anionic, π-system throughwhich the group is bound to M, and which group is also bound to 2; Z isa moiety bound to M via σ-bond, comprising boron, and the members ofGroup 14 of the Periodic Table of the Elements, and also comprising anelement selected from the groups consisting of an element selected fromthe groups consisting of nitrogen, phosphorus, sulfur and oxygen, saidmoiety having up to 60 nonhydrogen atoms; and X is a neutral, conjugatedor nonconjugated diene, optionally substituted with one or more groupsselected from hydrocarbyl or trimethylsilyl groups, said X having up to40 carbon atoms and forming a π-complex with M.
 29. The polyolefincopolymer composition of claim 26 wherein the metallocene complex of thecatalyst has a central metal Ti in which the formal oxidation state is+3 or +4.
 30. The polyolefin copolymer composition of claim 1 whereinthe composition has been produced with a bis-Cp metallocene catalyst.31. The polyolefin copolymer composition of claim 30 wherein thecomposition has been produced with a bridged bis-Cp metallocenecatalyst.
 32. The polyolefin copolymer composition of claim 31 whereinthe composition has been produced with a catalyst having a metallocenecomplex of the formula:

wherein Cp¹, Cp² are independently a substituted or unsubstitutedindenyl or hydrogenated indenyl group; Y is a univalent anionic ligand,or Y₂ is a diene; M is zirconium, titanium or hafnium; and Z is abridging group comprising an alkylene group having 1 to 20 carbon atomsor a dialkyl silyl- or germyl-group, or alkyl phosphine or amineradical.
 33. The polyolefin copolymer composition of claim 1 wherein thecatalyst has a single metallocene complex.
 34. The polyolefin copolymercomposition of claim 1 wherein the catalyst is supported on a supportmaterial.
 35. The polyolefin copolymer composition of claim 34 whereinthe support material is an inorganic oxide or magnesium halide.
 36. Thepolyolefin copolymer composition of claim 35 wherein the supportmaterial is silica, alumina, silica-alumina, or a mixture thereof. 37.The polyolefin copolymer composition of claim 36 wherein the supportmaterial is silica.
 38. The polyolefin copolymer composition of claim 34wherein the support material is a polymer.
 39. The polyolefin copolymercomposition of claim 1 wherein the process is a continuous processconducted in a single gas phase reactor.
 40. The polyolefin copolymercomposition of claim 1 wherein the composition is produced in a reactorwith a reaction zone having a temperature of 60° C. or higher.
 41. Thepolyolefin copolymer composition of claim 40 wherein the composition isproduced in a reactor with a reactor zone having a temperature of 70° C.or higher.
 42. The polyolefin copolymer composition of claim 1 whereinthe comonomer to monomer molar ratio is less than 0.02.
 43. Thepolyolefin copolymer composition of claim 1 wherein the hydrogen tomonomer molar ratio is less than 0.02.
 44. The polyolefin copolymercomposition of claim 1 wherein the composition has a short chainbranching distribution that is multimodal, or wherein the compositionhas a molecular weight distribution that is multimodal.
 45. Thepolyolefin copolymer composition of claim 1 wherein the density of thecomposition is from 0.910 to 0.925, the comonomer to monomer molar ratiois less than 0.02, the hydrogen to monomer ratio is less than 0.02, andthe composition is produced in a reactor with a reaction zone having atemperature of 70° C. or higher.
 46. A polyolefin copolymer compositionaccording to claim 1 produced in a continuous gas phase process.
 47. Apolyolefin copolymer composition according to claim 1 produced with acatalyst having a bis-Cp metallocene complex.
 48. A polyolefin copolymercomposition according to claim 1 produced with a catalyst having anorganometallic compound.
 49. A process for the polymerization of anα-olefin monomer with one or more olefin comonomers using a metallocenecatalyst in a single reactor, the composition having long chain branchesalong the polymer backbone and a molecular weight maximum which occursin that 50 percent by weight of the composition which has the highestweight percent comonomer content, as expressed by having a comonomerpartitioning factor C_(pf) which is equal to or greater than 1.10,and/or a molecular weight partitioning factor M_(pf) which is equal toor greater than 1.15, where the comonomer partitioning factor C_(pf) andthe molecular weight partitioning factor M_(pf) are as defined inclaim
 1. 50. A continuous gas phase process for the polymerization of anα-olefin monomer with one or more olefin comonomers using a catalysthaving a metallocene complex in a single reactor, the process producinga composition having a comonomer partitioning factor C_(pf) which isequal to or greater than 1.10, and/or a molecular weight partitioningfactor M_(pf) which is equal to or greater than 1.15, where thecomonomer partitioning factor C_(pf) and the molecular weightpartitioning factor M_(pf) are as defined in claim
 1. 51. A process forthe polymerization of an α-olefin monomer with one or more olefincomonomers using a catalyst having a bis-Cp metallocene complex in asingle reactor, the process producing a composition having a comonomerpartitioning factor C_(pf) which is equal to or greater than 1.10,and/or a molecular weight partitioning factor M_(pf) which is equal toor greater than 1.15, where the comonomer partitioning factor C_(pf) andthe molecular weight partitioning factor M_(pf) are as defined inclaim
 1. 52. An organometallic polymerization catalyst suitable for acontinuous gas phase polymerization process for the copolymerization of1-hexene and ethylene in a molar ratio of 0.02 or less at a temperatureof 70° C. and an ethylene pressure of 8 bar which produces a polyolefincopolymer composition having a density of 0.918, wherein the compositionhas long chain branches along the polymer backbone, or a molecularweight maximum which occurs in that 50 percent by weight of thecomposition which has the highest weight percent comonomer content, orwherein the composition has long chain branches along the polymerbackbone and a molecular weight maximum which occurs in that 50 percentby weight of the composition which has the highest weight percentcomonomer content.
 53. A film or other article of manufacture producedwith the polyolefin copolymer composition of claim 1 which has a meltstrength of greater than 4 cN, or which has a seal strength of greaterthan 1.9 kg (4.2 lb.), or which has a hot tack greater than 0.23 kg (0.5lb.), or which has a dart impact strength greater than 100 g.
 54. Ablend of two or more resin component comprising: (A) from 1 weightpercent to 99 weight percent of a polyolefin copolymer compositionaccording to claim 1; and (B) from 99 weight percent to 1 weight percentof one or more resins that are different from the (A) component.
 55. Theblend of claim 54 wherein the blend comprises from 1 weight percent to30 weight percent of component (A) and from about 99 weight percent to70 weight percent of component (B).
 56. The blend of claim 55 whereinthe blend comprises from 1 weight percent to 15 weight percent ofcomponent (A) and from 99 weight percent to 85 weight percent ofcomponent (B).
 57. The blend of claim 54 wherein the blend comprisesfrom 1 weight percent to 30 weight percent of component (B) and from 99weight percent to 70 weight percent of component (A).
 58. The blend ofclaim 57 wherein the blend comprises from 1 weight percent to 15 weightpercent of component (B) and from 99 weight percent to 85 weight percentof component (A).